CN104371051B - Butene-1 polymerization catalyst, and preparation and applications thereof - Google Patents

Abstract

The present invention relates to a butene-1 polymerization catalyst, preparation and applications thereof. According to the catalyst, anhydrous magnesium chloride is adopted as a carrier, titanium tetrachloride loaded on the magnesium chloride is adopted as an active component, an electron donor compound is adopted as a modifier, the content of the loaded component Ti is 1.50-4.20 wt%, and the content of the electron donor compound is 0.10-6.56 wt%. The catalyst is used for butene-1 homopolymerization. With the method, the problems of not high activity, low polymer isotacticity, difficultly-controllable polymer molecular weight distribution and hydrogen modulation insensitivity of the general catalyst are solved, and different electron donors, particularly the compound concurrently containing the ether ester bond, is added during the catalyst preparation to produce the polybutene-1 resin with characteristics of controllable polymer isotacticity, controllable polymer molecular weight and controllable polymer molecular weight distribution so as to improve the product performance, improve the resin processability, and broaden the product applications.

Description

A kind of catalyst of butene-1 polymerization and its preparation and application

Technical field

The present invention relates to a kind of catalyst of butene-1 polymerization and preparation method thereof, and answering in butene-1 polymerization With producing different isotacticities and the regulatable PB Polybutene-1 of molecular weight distribution.

Background technology

PB Polybutene-1 is, with butene-1 monomer as raw material, to be gathered using slurry process, vapor phase method or substance law in the presence of catalyst Close and made by.It is a kind of semicrystalline polyolefins thermoplastic resin, with good mechanical performance；Prominent environmental stress resistance Cracking behavior and thermostability；Excellent creep resistance, curls and continuous repeatedly, even if also having when temperature is improved good anti-compacted Degeneration；Good resistance to chemical corrosion；And the wearability close with ultra-high molecular weight polyethylene；High filler fillibility etc..Cause This can be used for production pipeline, thin film, sheet material and various containers etc., particularly it can at a temperature of 90～100 DEG C life-time service.

It is external more to the research of PB Polybutene-1, in the sixties in 20th century of industrialized PB Polybutene-1 mainly synthesis etc. The vertical structure of rule（Isotacticity is higher than 90%）, high-crystallinity（Degree of crystallinity is 50～60%）PB Polybutene-1 plastics（PB）.Substantially adopt With prepare polypropylene（PP）Similar production technology and catalyst system and catalyzing.Nineteen eighty-two, European patent EP 82111264.6 is reported first A kind of to adopt the modified load titanium catalyst system to synthesize isotacticity for 70～80%, degree of crystallinity is 25～40%, with thermoplasticity The PB of elastomer properties.Its performance is similar to EPDM/PP, SEBS hot plastomer and plasticized PVC soft material, can replace in many occasions Their purposes, so as to expand the purposes and value of PB.It has the disadvantage that PB isotacticities are relatively low, limits its application.

European patent EP 187034A2 adopts low hydrocarbon (such as normality butane, iso-butane, Pentamethylene .) for solvent, and Ziegler-Natta catalyst, and organo-aluminum compound, and external electron donor (such as DDS and CHMMS), and butene-1 exists It is polymerized at 20～45 DEG C, prepares high stereospecific PB Polybutene-1.Need in the preparation method that this preparation method solves The problem to separate solvent from butene polymers.The advantage of this preparation method is to be not required in its preparation process Non- stereospecific polybutylene polymer to be separated, because the isotaxy value of the polybutylene polymer of the method preparation is up to 80% More than, and the polybutylene polymer easily separation from solvent.However, due to aforesaid Catalyst Conversion it is relatively low, (2360g/g Cat4h, i.e. 590g/g Cath), in order to avoid deteriorating the thing of obtained polymer the step of need a separating catalyst residue Rationality energy.Meanwhile, above-mentioned manufacture method for it is large batch of for commodity production for polymerization activity it is still too low.

TiCl is adopted in European patent EP 0201647A1₄/DNBP/Mg(C₂H₅O)₂-AlEt₃/ phenyl triethoxysilane is urged Change system catalyzing butene -1 is polymerized, polymerization activity up to 2667gPB/gCat3.8h, i.e. 701gPB/g Cath, poly- fourth The bulk density of alkene -1 is 0.30g/cm³.Although the preparation method has obtained graininess PB Polybutene-1, its polymerization activity is too It is low, in order to avoid deteriorating the physical property of obtained polymer the step of need a separating catalyst residue.

TiCl is adopted in US6306996B1 (CN1256698A)₄/ DNBP/ ball-type magnesium chloride (MgCl₂·2.1C₂H₅OH)- AlEt₃(or AlⁱBu₃)/diisopropyl dimethoxy silane (DIPMS) catalyst system and catalyzing, and using butene-1 itself as solvent and Reaction monomers, have prepared high stereospecific PB Polybutene-1 of the isotacticity higher than 95%, and the ppm contents of the titanium in polymer are less than 50, and molecular weight distribution >=6, catalysis activity is 3500g/g Cath.However, the catalysis activity of the preparation method is still much Less than those efficient polyethylene and the preparation method of polyacrylic polymer, therefore the productivity ratio of the method is relatively low. US7345122bB2 (CN1590417A (Ylem Technology Holdings Inc. of Korea)) adopts TiCl₄/ the 1,3- containing silicon atom Diether/anhydrous magnesium chloride/isooctanol-AlEt₃(or AlⁱBu₃)/silanes external electron donor (such as DPDMS and DIBDMS) is catalyzed System, has obtained PB Polybutene-1 of the isotacticity higher than 98%, and polymerization activity is in 9800～20000gPB/g Cath, polymer point Son amount is distributed between 4～6.Although the catalysis activity of the preparation method and polymer isotacticity are higher, high-volume can be met Commercially produce, but molecular weight distribution is narrower, is unfavorable for the exploitation of more trade mark products.CN1374327A (three Well chemistry Zhu Shi societies) adopt TiCl₄/ 2- isopropyl -2- isobutyl group -1,3- dimethoxy propanes (or the isobutyl of phthalic acid two Ester)/anhydrous magnesium chloride/isooctanol-AlEt₃(or AlⁱBu₃)/silanes external electron donor (such as DPDMS and DIBDMS) is catalyzed System, has obtained the polybutene copolymer of isotacticity 91～95%, polymerization activity 4800g/gCath, molecular weight distribution Between 3.5～4.6.It can be seen that catalyst is active relatively low, and molecular weight distribution is narrower, is unfavorable for production effect The raising and the exploitation of more trade mark products of rate.At present, the domestic report with regard to butene-1 polymerization is also more, for example：1993 Wu Qing etc.^[13]Use TiCl₄,Ti(OBu)₄/MgCl₂/EB/Ph₂SiCl₂As catalyst, AlEt₃For promoter, have studied not Same polymerizing condition（Such as catalyst composition, temperature, external electron donor, H₂、AlEt₃, catalyst concn）Catalysis to butene-1 polymerization The impact of activity, the molecular weight of PB Polybutene-1 and isotacticity.Test result indicate that, catalysis activity is up to 3.2 × 10⁴g PB/gTi × h, hydrogen tonality is good, and polymer isotacticity is with p-CH in catalyst system and catalyzing₃C₆H₄The increase of COOEt and improve, up to 93.3%(Diao J B,Wu Q,Lin S A.J Polym Sci,Part A:Polym Chem,1993,31(9):2287～ 2293)；The Huang Bao treasures research department of Qingdao University of Science and Technology is always worked on for many years in the research of butene-1 polymer material, is adopted TiCl₄Double (methoxy) fluorenes/MgCl of/9,9-₂-AlEt₃/ DDS catalyst system and catalyzings are successfully prepared for height entirely with the poly- fourth of content The material of alkene -1 (Bi Fuyong, Yao Wei, yellow treasured treasure etc. elastomer, 2007,17 (1):40～44；Huang Baochen, Yao Wei etc. it is high complete with poly- The bulk depositing synthesis process .CN101020728A of butene-1,2007).But scientific research aspect is all confined to, and is really realized Industrialized report does not then have.

From the above, it can be seen that the electron donor for using is ethyl benzoate, dibutyl phthalate, O-phthalic Sour diisobutyl ester, or 2- isopropyl -2- isobutyl group -1,3- dimethoxy propanes and 1, the 3- diether containing silicon atom.Though Right two esters electron donor activity is not as two ethers, but molecular weight distribution is wider, is conducive to improving the processability of product；Two Though ethers electron donor activity is high, capacity of orientation is strong, and its molecular weight distribution is narrower, is unfavorable for the processing of product and more voluminous The exploitation of brand number.But for the new electron donor being good for containing ether in same compound and ester is good for, two esters and two The compounding of both ethers electron donors, and new phthalate electron donor do not appear in the newspapers to the impact that butene-1 is polymerized Road.

The content of the invention

It is an object of the invention to provide a kind of catalyst of butene-1 polymerization and its preparation and application.By in catalyst system Standby middle addition electron donor compound (including ether ester compound and new phthalate compound) or ether/ester compounding Electron donor produces molecular weight and the adjustable PB Polybutene-1 resin of molecular weight distribution, is processed into so as to enhancing product performance, reducing Originally, olefin polymer application is widened.This catalyst avoids two ethers, the shortcoming of two two kinds of catalyst of esters, gives full play to Its respective advantage, so that catalyst system has high activity, high directionality, good hydrogen tonality.

A kind of catalyst of butene-1 polymerization of the present invention, the catalyst loads chlorine with anhydrous magnesium chloride as carrier Change the titanium tetrachloride on magnesium carrier as active component, electron donor compound is used as modifying agent, and it is whole that load component accounts for catalyst Weight percentage composition is Ti：1.50～4.20wt%, electron donor：0.10～6.56wt%.

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

(1) under argon gas atmosphere protection, in the reactor with mechanical agitator, alkane solvent, anhydrous is sequentially added Magnesium chloride and Organic Alcohol, react 2 hours at then heating to 130 DEG C, obtain homogeneous reaction thing A,

Wherein, the consumption of alkane is 20mL/g anhydrous magnesium chlorides, and Organic Alcohol is 2.0～6 with the mol ratio of anhydrous magnesium chloride： 1, Organic Alcohol is one or two mixture in C2～C8 alcohol, preferred butanol and isooctanol, and magnesium alkoxide mol ratio is preferably 3.0～6.0：1；

(2) above-mentioned reactant A solution is added into 1g phthalic anhydrides (PA) or four titanium butoxide acid esters (Ti (BuO)₄), and here temperature The lower reaction of degree 2 hours, obtains reactant B, and is cooled to room temperature, and (3) will in 2 hours by all reactant Bs obtained above It is added drop-wise to the 100mL TiCl that temperature remains -10 DEG C₄In solution, mixture temperature is set to keep 0.5 at -10 DEG C after dripping off Hour, then in 6 hours temperature is carried to 110 DEG C under agitation, and this temperature is kept for 2 hours, obtain reactant mixture C,

(4) reactant mixture C is carried out into heat filtering separation, obtains solid product D,

(5) 100mL TiCl will be added in solid D again₄Solution, carries temperature to 100 DEG C, adds electron donor, continues to rise Temperature keeps this temperature 2 hours to 110 DEG C, obtains reactant mixture E, and reactant mixture E is carried out heat filtering separation by (6), Solid product F is obtained,

(7) solid product F is fully washed with normal hexane at 60 DEG C, until inspection does not measure precipitation in cleanout fluid Titanium compound, so obtain solid titanium catalyst.

Electron donor described in above-mentioned catalyst preparation step (5) is ethyl benzoate (EB), diethyl phthalate (DEP), dibutyl phthalate (DNBP), diisobutyl phthalate (DIBP), dicyclohexyl phthalate (DCHP), diisooctyl phthalate (DIOP), the peopentyl ester of phthalic acid two (DPP), benzoic acid (2- methoxyl groups) ethyl ester (MOEB), phthalic acid two (2- methoxyl groups) ethyl ester (PBMOE), ethyl phenyl ether (MPE), glycol dimethyl ether (EGDE), 4- first Base n-butyl phthalate (MDNBP), 4- methylphthalic acid diisobutyl esters (MDIBP), 4- methylphthalic acids Di-isooctyl (MDIOP), the peopentyl ester of 4- methylphthalic acids two (MDPP), 4- phthalate bromine dibutyl esters (BrDNBP), 4- phthalate bromine diisobutyl esters (BrDIBP), 4- phthalate bromine di-isooctyls (BrDIOP) or 4- phthalate bromines Two peopentyl esters (BrDPP) etc..

The application of catalyst described above, for butene-1 homopolymerization synthesis PB Polybutene-1 (PB), its step is as follows：

2L rustless steels stirred tank is replaced 3 times with high-purity argon gas at the polymerization temperature, is replaced 1 time with butene-1.High-purity Under argon protection, the purified normal hexane of 1L and a certain amount of external electron donor, 1.0mol/L triethyl aluminum hexane solutions are added, It is subsequently adding the hexane suspension of appropriate solid catalyst.Then being passed through hydrogen (needs) to the system, then be passed through butene-1 makes Stagnation pressure is 0.8MPa (gauge pressure) successive reaction 2 hours.After the completion of polymerization, with 100mL ethanol terminating reactions, washing, filtration polymerization Thing, and constant weight is dried under vacuum at 60 DEG C, weigh and calculate activity.

Beneficial effect：

The invention provides a kind of be suitable to catalyst component that butene-1 is polymerized and preparation method thereof, and this catalyst exists Application in butene-1 polymerization, produces different isotacticities and the regulatable PB Polybutene-1 of molecular weight distribution,

1. solve the problems, such as that general catalyst activity is not high.Embodiment from this patent can compared with comparative example 1 If with it is clear to see that in the case of using identical electron donor, the catalysis done according to United States Patent (USP) US7345122bB2 The activity of agent is only 9800～20000gPB/g Cath, and its activity has very big using the catalyst of this patent method preparation The raising of degree, catalyst activity is up to 26.7 × 10³gPB/g Cat·h.In addition, making in United States Patent (USP) US7345122bB2 Standby catalyst needs three load titaniums, and catalyst prepared by this patent is secondary load titanium, and catalyst preparation flow process is greatly simplified, Be conducive to cost-effective.

2. solve the problems, such as that the polymer isotacticity prepared by general catalyst is difficult to.Enforcement from this patent , it is apparent that by adding different types of internal electron donor and its adjustment addition, or polymerization in catalyst in example When add different types of external electron donor and its adjustment addition, or polymerization when add different amounts of hydrogen etc., make polymerization The isotacticity of thing can be controlled between 80%～99%.

3. the molecular weight and molecular weight distribution for solving the problems, such as general polymerization thing is difficult to.With in difference in this patent Controlling molecular weight and its distribution of polymer, the molecular weight for alloing polymer is controlled for electron donor and added hydrogen 20×10⁴～120 × 10⁴G/mol, and molecular weight distribution can regulate and control between 3.5～14.So as to improve adding for resin Work, the performance that improve product, the application for having widened product.

Specific embodiment

It is as follows about the assay method of catalyst composition obtained in each embodiment：

Ti contents are determined with UV detector (CARY-300) in catalyst

Electron donor content is determined with gas chromatograph (SP3420) in catalyst

Polymerization activity is calculated as follows：

W_poly=Q/w_cat, gPolyg^-1Cat, wherein W_polyFor polymerization catalyst activity, Q is in polyreaction 2 hours The yield (g) of polymer, w_catFor catalyst amount.

It is as follows about the test condition of polymer：

Isotacticity I.I. --- percetage by weight shared by insoluble matter after ether extraction

Heap density BD --- ASTM D1895

Molecular weight Mw --- gas phase gel permeation chromatography (PL-220)

Molecular weight distribution mw/mn --- gas phase gel permeation chromatography (PL-220)

Embodiment 1

(1) under high-purity argon gas protection, to sequentially add in churned mechanically reactor 60mL n-decanes, 3.0g without Aqueous magnesium chloride and 12.4mL isooctanol, are warming up to 130 DEG C of reaction 2h, obtain a kind of homogeneous phase solution A,

(2) above-mentioned reactant A solution is added into 1g phthalic anhydrides (PA), and is reacted 2 hours at 130 DEG C, obtain reactant B, And it is cooled to room temperature,

(3) all reactant Bs obtained above were added dropwise to into the 100mL that temperature remains -10 DEG C in 2 hours TiCl₄In solution, mixture temperature is set to keep at -10 DEG C after dripping off 0.5 hour, then under agitation in 6 hours temperature Degree is carried to 110 DEG C, and this temperature is kept for 2 hours, obtains reactant mixture C,

(4) reactant mixture C is carried out into heat filtering separation, obtains solid product D,

(5) 100mL TiCl will be added in solid D again₄Solution, carries temperature to 100 DEG C, adds internal electron donor neighbour's benzene Dioctyl phthalate two (2- methoxyl groups) ethyl ester (PBMOE) 1.58mmol, is continuously heating to 110 DEG C, and this temperature is kept for 2 hours, obtains To reactant mixture E,

(6) reactant mixture E is carried out into heat filtering separation, obtains solid product F,

(7) solid product F is fully washed with normal hexane at 60 DEG C, until inspection does not measure precipitation in cleanout fluid Titanium compound, so obtain solid titanium catalyst.Each component weight/mass percentage composition is Ti=2.77%, PBMOE=in catalyst 3.79%。

Polymerization is characterized：

At the polymerization temperature, 2L rustless steels stirred tank is replaced 3 times with high-purity argon gas, is replaced 1 time with butene-1.High-purity The purified normal hexane of the lower addition 1L of argon protection, 0.05mmol Cyclohexyl Methyl Dimethoxysilanes (CHMMS), Solid catalyst 1.0mmol triethyl aluminums and 0.005mmol (based on titanium atom) obtained above, catalyst is adding polymeric kettle Before, reactor is injected after forming slurry with 10mL normal hexane under argon protection.Then the hydrogen of 0.05MPa is passed through to the system Gas (if desired for), then being passed through butene-1 makes stagnation pressure be 0.8MPa (gauge pressure) successive reaction 2 hours.After the completion of polymerization, 100mL second is used Alcohol terminating reaction, washing, filtered polymeric, and constant weight is dried under vacuum at 60 DEG C, obtain the poly- fourth of 320g globular solids granules Alkene -1, it is 32.0 × 10 to calculate its activity³GPB/gCat, bulk density：0.42g/cm³, isotacticity is 98%, molecular weight Mw=65 ×10⁴G/mol, molecular weight distribution PD=5.41.

The method for preparing catalyst and polymerization characterizing method of embodiment 2～11 is with embodiment 1, the thing added in concrete preparation Matter and addition are shown in Table 1, and its polymerization result is shown in Table 2.

Each component content in material, consumption and catalyst that the catalyst preparation of table 1 is added

Comparative example 1

Catalyst preparation：

(1) under high-purity argon gas protection, to sequentially add in churned mechanically reactor 60mL n-decanes, 3.0g without Aqueous magnesium chloride and 12.4mL isooctanol, are warming up to 130 DEG C of reaction 2h, obtain a kind of homogeneous phase solution A,

(2) above-mentioned reactant A solution is added into 1g phthalic anhydrides (PA), and is reacted 2 hours at 130 DEG C, obtain reactant B, And it is cooled to room temperature,

(3) all reactant Bs obtained above were added dropwise to into the 100mL that temperature remains -10 DEG C in 2 hours TiCl₄In solution, mixture temperature is set to keep at -10 DEG C after dripping off 0.5 hour, then under agitation in 6 hours temperature Degree is carried to 110 DEG C, and this temperature is kept for 2 hours, obtains reactant mixture C,

(4) reactant mixture C is carried out into heat filtering separation, obtains solid product D,

(5) 50mL toluene solutions and 50mL TiCl will be added in solid D again₄Solution, carries temperature to 100 DEG C, adds interior Electron donor O-phthalic diisobutyl ester (DIBP) 0.28ml, is continuously heating to 110 DEG C, and this temperature is kept for 2 hours, obtains Reactant mixture E,

(6) reactant mixture E is carried out into heat filtering separation, obtains solid product F,

(7) 50mL n-heptane solutions and 50mL TiCl will be added in solid product F again₄Solution, reacts 2 hours at 98 DEG C, Reactant mixture G is obtained,

(8) reactant mixture G is carried out into heat filtering separation, obtains solid product H,

(9) solid product H is fully washed with normal hexane at 60 DEG C, until inspection does not measure precipitation in cleanout fluid Titanium compound, so obtain solid titanium catalyst.Each component weight/mass percentage composition is Ti=1.97%, DIBP=in catalyst 3.79%。

Polymerization is characterized：

At the polymerization temperature, 2L rustless steels stirred tank is replaced 3 times with high-purity argon gas, is replaced 1 time with butene-1.High-purity The purified normal hexane of the lower addition 1L of argon protection, 0.0125mmol Cyclohexyl Methyl Dimethoxysilanes (CHMMS), Solid catalyst 0.25mmol triethyl aluminums and 0.005mmol (based on titanium atom) obtained above, catalyst is adding polymerization Before kettle, after forming slurry with 10mL normal hexane under argon protection reactor is injected.Then it is passed through 0.05MPa's to the system Hydrogen (if desired for), then being passed through butene-1 makes stagnation pressure be 0.8MPa (gauge pressure) successive reaction 2 hours.After the completion of polymerization, 100mL is used Ethanol terminating reaction, washing, filtered polymeric, and constant weight is dried under vacuum at 60 DEG C, and 124g solid PB Polybutene-1s are obtained, count It is 10.2 × 10 to calculate its activity³GPB/gCat, isotacticity is 94%, molecular weight Mw=65 × 10⁴G/mol, molecular weight distribution PD= 8.22。

Embodiment 12

Repeat the process of embodiment 1, simply external electron donor is changed to into dimethoxydiphenylsilane (DDS), other Part is constant, and the results are shown in Table 2 for it.

Embodiment 13

Repeat the process of embodiment 8, simply amounts of hydrogen is increased to into 0.15MPa, other conditions are constant, and its result is listed in table In 2.

Embodiment 14

Repeat the process of embodiment 6, simply change promoter into triisobutyl aluminium, other conditions are constant, its result row In table 2.

The polymerization of the different catalysts of table 2 is characterized

Summarize：The embodiment 9 of electron donor DIBP identical for addition, can be with it is clear to see that real compared with comparative example 1 The catalyst preparation process applied in example is not only simple, and the activity of catalyst is high.Additionally, adding in catalyst preparation not of the same race The electron donor of class or varying number, it will be apparent that (activity of catalyst is 20.4 × 10 to improve catalyst activity³～54.7 × 10³Between g/gCat), and the isotacticity (I.I. of polymer：81%～99%) and molecular weight distribution (Mw/Mn：4.53～ 13.62) controllable effect, so as to the machinability for improving resin, the performance that improve product, the application neck for having widened product Domain.

Claims (5)

1. the catalyst that a kind of butene-1 is polymerized, it is characterised in that：The catalyst is supported on chlorination with anhydrous magnesium chloride as carrier Titanium tetrachloride on magnesium carrier is active component, and electron donor compound is modifying agent, and load component accounts for catalyst total quality Percentage composition is Ti：1.50～4.20wt%, electron donor compound：0.10～6.56wt%；What the butene-1 was polymerized urges The preparation method of agent comprises the steps：(1) under argon gas atmosphere protection, in the reactor with mechanical agitator, according to Secondary addition alkane solvent, anhydrous magnesium chloride and Organic Alcohol, react 2 hours at then heating to 130 DEG C, obtain homogeneous reaction thing A； Wherein, the consumption of alkane is 20mL/g anhydrous magnesium chlorides, and Organic Alcohol is 2.0～6 with the mol ratio of anhydrous magnesium chloride：1, Organic Alcohol It is one or two mixture in C2～C8 alcohol；(2) reactant A solution is added into 1g phthalic anhydrides or four butoxy metatitanic acids Ester, and react 2 hours at 130 DEG C, reactant B is obtained, and it is cooled to room temperature；(3) reactant B was added drop-wise to into temperature in 2 hours Degree remains -10 DEG C of 100mLTiCl₄In solution, mixture temperature is set to be kept for 0.5 hour at -10 DEG C after dripping off, Ran Hou Under stirring temperature is carried to 110 DEG C in 6 hours, and this temperature is kept for 2 hours, obtain reactant mixture C；(4) will reaction Mixture C carries out heat filtering separation, obtains solid product D；(5) 100mLTiCl will be added in solid D again₄Solution, puies forward temperature To 100 DEG C, electron donor is added, be continuously heating to 110 DEG C, and this temperature is kept for 2 hours, obtain reactant mixture E；(6) Reactant mixture E is carried out into heat filtering separation, solid product F is obtained；(7) solid product F is carried out with normal hexane at 60 DEG C Fully washing, until inspection does not measure the titanium compound of precipitation in cleanout fluid, so obtains solid titanium catalyst.

2. described in a kind of claim 1 butene-1 polymerization catalyst preparation method, it is characterised in that：Including following step Suddenly：(1) under argon gas atmosphere protection, in the reactor with mechanical agitator, alkane solvent, anhydrous magnesium chloride are sequentially added And Organic Alcohol, react 2 hours at then heating to 130 DEG C, obtain homogeneous reaction thing A；Wherein, the consumption of alkane be 20mL/g without Aqueous magnesium chloride, Organic Alcohol is 2.0～6 with the mol ratio of anhydrous magnesium chloride：1, Organic Alcohol be the one kind in C2～C8 alcohol or Two kinds of mixture；(2) reactant A solution is added into 1g phthalic anhydrides or four titanium butoxide acid esters, and is reacted 2 hours at 130 DEG C, obtained Reactant B, and it is cooled to room temperature；(3) reactant B was added drop-wise to into the 100mLTiCl that temperature remains -10 DEG C in 2 hours₄It is molten In liquid, make mixture temperature keep 0.5 hour at -10 DEG C after dripping off, then under agitation in 6 hours temperature carry to 110 DEG C, and this temperature is kept for 2 hours, obtain reactant mixture C；(4) reactant mixture C is carried out into heat filtering separation, is obtained Solid product D；(5) 100mLTiCl will be added in solid D again₄Solution, carries temperature to 100 DEG C, adds electron donor, continues 110 DEG C are warming up to, and this temperature is kept for 2 hours, obtain reactant mixture E；(6) reactant mixture E is carried out into heat filtering point From obtaining solid product F；(7) solid product F is fully washed with normal hexane at 60 DEG C, until examining in cleanout fluid The titanium compound of precipitation is not measured, solid titanium catalyst is so obtained.

3. the preparation method of the catalyst being polymerized according to the butene-1 described in claim 2, it is characterised in that：Institute in step (5) State electron donor for ethyl benzoate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, Dicyclohexyl phthalate, diisooctyl phthalate, the peopentyl ester of phthalic acid two, benzoic acid (2- methoxyl groups) second Ester, phthalic acid two (2- methoxyl groups) ethyl ester, ethyl phenyl ether, glycol dimethyl ether, 4- methylphthalic acid di-n-butyls, 4- Methylphthalic acid diisobutyl ester, 4- methylphthalic acid di-isooctyls (MDIOP), 4- methylphthalic acids two new penta Ester, 4- phthalate bromine dibutyl esters, 4- phthalate bromine diisobutyl esters, 4- phthalate bromines di-isooctyl or 4- bromines are adjacent The peopentyl ester of phthalic acid two.

4. the application of the catalyst of the butene-1 polymerization described in a kind of claim 1, it is characterised in that：For butene-1 homopolymerization, Step is as follows：2L rustless steels stirred tank is replaced 3 times with high-purity argon gas at the polymerization temperature, is replaced 1 time with butene-1, high-purity Under argon protection, the purified normal hexane of 1L and external electron donor, 1.0mol/L triethyl aluminum hexane solutions are added, be subsequently adding The hexane suspension of solid catalyst, then be passed through butene-1 to make stagnation pressure to the system is gauge pressure 0.8MPa, or to the system Being passed through hydrogen, then be passed through butene-1 makes stagnation pressure for gauge pressure 0.8MPa, successive reaction 2 hours；After the completion of polymerization, 100mL ethanol is used Terminating reaction, washing, filtered polymeric, and constant weight is dried under vacuum at 60 DEG C, weigh and calculate activity；Wherein, material proportion For：Molar ratio computing aluminum alkyl catalyst triethyl aluminum：External electron donor：Catalyst=200：10：1, catalyst amount is 0.005mmol/mL normal hexane.

5. the application of the catalyst of the butene-1 polymerization described in a kind of claim 1, it is characterised in that：With slurry polymerization or body Polymerization can directly obtain spherical solid.