CN101153062A - A kind of olefin polymerization solid catalyst component and its preparation method and application - Google Patents

Abstract

A solid catalyst component for olefin polymerization, comprising a titanium compound loaded on a magnesium compound carrier and an internal electron donor, the internal electron donor comprising dialkyl phthalate and selected from formula (I) or (II ) ether compound, the mass ratio of ether to ester is 0.1-3.0:1, in formula (I) or (II), R ₁ is selected from C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ Cycloalkyl, C ₆ -C ₂₀ aryl, alkaryl or aralkyl, R ₂ is selected from hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₂₀ aryl, alkaryl or aralkyl, R ₃ is selected from hydrogen, C ₁ to C ₁₂ alkyl, C ₃ to C ₁₂ cycloalkyl, C ₆ to C ₂₀ aryl or alkaryl . The solid catalyst has high activity for olefin polymerization, and the obtained polyolefin molecular weight distribution is wide.

Description

A kind of olefin polymerization solid catalyst component and its preparation method and application

technical field

The invention relates to an olefin polymerization solid catalyst component, its preparation method and application, specifically, a solid catalyst component containing an internal electron donor compound, its preparation method and its application in olefin polymerization.

Background technique

CH ₂ =CHR The solid catalyst component used in the polymerization of olefins, especially α-olefins having 3 carbon atoms or more, contains the basic components of magnesium, titanium, halogen and electron donor compounds, wherein the electron donor The body compound is mostly called the internal electron donor, which is mainly used to improve the stereoregularity of the polymer. The internal electron donor compounds used in the prior art include polycarboxylic acids, monocarboxylic esters, polycarboxylic acid esters, acid anhydrides, ketones, ethers, alcohols or amines, among which polycarboxylic acid esters are commonly used.

In recent years, people try to adopt other compounds as the electron donor in the olefin polymerization solid catalyst component again, as in the olefin polymerization solid catalyst component described in CN1042547A and CN1143651A, the internal electron donor compound that adopts is to contain two ethers Group 1,3-diether compounds, such as 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethyl Oxypropane and 9,9-bis(methoxymethyl)fluorene, etc.

Recently, it has been reported that in the olefin polymerization solid catalyst, the use of a dibasic aliphatic carboxylic acid ester compound with a special structure is an internal electron donor, such as CN1313869A, CN1236373A, CN1236374A, CN1242780A, CN1453298A use succinate, Malonate, glutarate, cyano ester and glycol ester are internal electron donor compounds, and CN1597714A and CN1398270A use two electron donor compounds compounded as internal electron donors. The use of these electron donors can not only improve the activity of the catalyst, but also significantly broaden the molecular weight distribution of the obtained propylene polymer.

The olefin polymerization catalyst prepared by the internal electron donor compound disclosed by the above method still has certain problems in practical application, such as the activity of the catalyst adopting dibasic aromatic carboxylic acid ester compound as the internal electron donor is low, and the obtained polymerization The molecular weight distribution of the compound is also narrow; the catalyst activity of the dibasic aliphatic carboxylic acid ester compound is also low; although the catalyst of the 1,3-diether compound is highly active and the hydrogen adjustment sensitivity is also good, but The molecular weight distribution of the obtained polymer is narrow, which is not conducive to the development of different grades of polymer products.

Contents of the invention

The object of the present invention is to provide a solid catalyst component for olefin polymerization. The solid catalyst component has high catalytic activity for olefin polymerization and the obtained polymer has high isotacticity and wide molecular weight distribution.

Another object of the present invention is to provide a method for preparing the above-mentioned catalyst component and a method for olefin polymerization using it.

The olefin polymerization solid catalyst component provided by the present invention includes a titanium compound supported on a magnesium compound carrier and an internal electron donor, the magnesium content in the catalyst is 15-25% by mass, the titanium content is 1.0-10.0% by mass, and the internal The electron donor content is 5-15% by mass, and the internal electron donor includes dialkyl phthalate and ether compounds selected from formula (I) or (II), and the mass ratio of ether to ester is 0.1～3.0:1,

In formula (I) or (II), R ₁ is selected from C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₂₀ aryl, alkaryl or aralkyl, R ₂ is a substituent on the benzene ring, each substituent may be the same or different, and R ₂ is selected from hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₂₀ Aryl, alkaryl or aralkyl, R ₃ is selected from hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₂₀ aryl or alkaryl.

The electron donor in the solid catalyst of the present invention adds a kind of ether to the commonly used ester compound, which improves the polymerization activity of the catalyst, especially in the propylene polymerization reaction, high isotacticity and wide molecular weight distribution can be obtained of polypropylene.

Detailed ways

The present invention adopts ethers converted from phenols as internal electron donor compounds, and compounded with dialkyl phthalates to prepare solid catalyst components. The solid catalyst is used for olefins, especially propylene polymerization, and has relatively high activity. High, and polypropylene with high isotacticity and wide molecular weight distribution (Mw/Mn) can be obtained.

In the ethers of formulas (I) and (II) provided by the present invention, R _is a group connected to the oxygen in phenol, which can be an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkaryl group, preferably C ₁ -C ₆ alkyl, phenyl or indenyl, more preferably C ₁ -C ₄ alkyl. R ₂ is 4 substituents on the benzene ring, and each substituent can be the same or different, preferably hydrogen or C ₁ -C ₆ alkyl, more preferably all 4 substituents are hydrogen, or the benzene ring 4 , the 6-position substituent is C ₁ -C ₆ alkyl, the 3- and 5-position substituents are hydrogen; or the 4-position substituent of the benzene ring is C ₁ -C ₃ alkyl, and the 6-position substituent is C ₃ -C ₆ is an alkyl group, and the substituents at the 3 and 5 positions are hydrogen. The R ₃ is a substituent connected to a carbonyl group in formula (I), preferably a phenyl group, an indenyl group, a C ₁ -C ₁₂ alkyl group or a C ₇ -C ₂₀ alkaryl group.

The magnesium compound in the solid catalyst component is a catalyst carrier, preferably magnesium chloride or an alcoholate of magnesium chloride. The titanium compound is the active component of the catalyst, selected from compounds with the general formula TiX _n (OR) _4-n , wherein R is an alkyl group of C ₁ to C ₈ , X is a halogen, and n is an integer of 1 to 4, Preferable are tetrabutoxytitanium, tetraethoxytitanium, monochlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, more preferably titanium tetrachloride.

The dialkyl phthalate is another electron donor in the solid catalyst, and the alkyl group in the dialkyl phthalate is preferably a C ₁ -C ₆ alkyl group.

The content of the internal electron donor in the solid catalyst component is preferably 5.0-15.0% by mass, wherein the mass ratio of the ether to the ester is preferably 0.5-1.0:1.

The preparation method of solid catalyst component of the present invention, comprises the steps:

(1) Place the magnesium compound carrier in an inert hydrocarbon to form a suspension, add the suspension to the titanium compound solution at 0 to -20°C, the titanium/magnesium molar ratio is 5 to 60:1, and heat up to 60 ~80°C, add the ether of formula (I) or (II) and dialkyl phthalate, fully react at 100~125°C, collect the solid, the magnesium/ether molar ratio is 5~25:1, Ether/ester molar ratio is 0.5～1.7,

(2) Add the solid to the titanium compound solution preheated to 100-125° C. to fully react, the titanium/magnesium molar ratio is 1-20:1, remove the liquid, and wash the obtained solid with inert hydrocarbon and dry.

In the method, the magnesium compound support in step (1) is preferably spherical magnesium chloride, the titanium compound is preferably titanium tetrachloride, and the alkyl group in the dialkyl phthalate is preferably a C ₁ -C ₆ alkyl group. The ratio of the inert hydrocarbon to the magnesium compound in the suspension is preferably 3.0-8.0 ml/g, and after being added to the titanium compound solution, the molar ratio of titanium/magnesium is preferably 5-30:1. (2) The molar ratio of the titanium compound added in the step to the magnesium in the carrier is preferably 3-10:1.

The inert hydrocarbon in the process is preferably hexane, heptane or straight-run gasoline. The solvent of the titanium compound solution is preferably toluene.

The spherical magnesium chloride carrier can be prepared by referring to the method of CN1109067A, and the alcohol content in the carrier is 1.5-4.0 moles of alcohol/mole of MgCl ₂ , preferably 2.0-3.0 moles of alcohol/mole of MgCl ₂ .

The ether compounds used in the present invention can be prepared by various methods, preferably by reacting the corresponding phenolic compound with a base, and then reacting with an excess of halogenated alkanes with the general formula R ₁ X. In the formula R ₁ X, R ₁ is selected from from C ₁ to C ₁₂ alkyl, C ₃ to C ₁₂ cycloalkyl, C ₆ to C ₂₀ aryl, alkaryl or aralkyl, preferably C ₁ to C ₆ alkyl, phenyl or Indenyl is more preferably a C ₁ -C ₄ alkyl group, and X is preferably iodine.

In the described method, the alkali that acts on the phenolic compound is preferably an alkali metal alkoxide, such as potassium tert-butoxide or potassium isopropoxide, and the temperature of the reaction between phenol and alkali is 0 to 100° C. In order to increase the solubility of the phenolic compound, A solvent should be added to the phenol, the preferred solvent being dioxane. During the reaction, the temperature of adding R ₁ X to carry out the reaction is preferably 0-100° C., and the molar ratio of added R ₁ X to phenolic compound is preferably 1.2-3.0:1.

The olefin polymerization method provided by the invention comprises using the solid catalyst described in the invention as a main catalyst and reacting olefins under polymerization conditions in the presence of a cocatalyst alkyl aluminum compound. The polymerization reaction can be carried out in liquid phase or gas phase, and can also be carried out under the operation of a combination of liquid phase and gas phase polymerization stages. The olefins are C ₂ -C ₂₀ α-olefins. The suitable polymerization reaction temperature is 0-150°C, preferably 30-90°C, and the pressure is 0.1-4.0MPa, preferably 0.5-3.0MPa.

The aluminum alkyl is preferably a compound with the general formula AlR' _n X _3-n , where R' is hydrogen or a C ₁ -C ₂₀ alkyl group, X is a halogen, and n is a number between 1 and 3. During the reaction, the aluminum/titanium molar ratio is 5-1000:1, preferably 25-500:1. Preferred aluminum alkyls are triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, monohydrogen diethylaluminum, monohydrogen diisobutylaluminum, monohydrogen diisobutylaluminum, Diethylaluminum chloride, diisobutyl chloride monochloride, sesquiethylaluminum chloride, or ethylaluminum dichloride.

In order to improve the isotacticity of the polymer, it is preferable to add an external electron donor during the polymerization reaction. The preferred external electron donor compound is selected from the general formula R ¹ _n Si(OR ² ) _4-n silane compounds, where 0≤n ≤3, R ¹ and R ² are respectively selected from C ₁ -C ₁₂ alkyl, cycloalkyl, aryl or haloalkyl. Preferred silane compounds are trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyl phenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane or methyl-tert-butyldimethoxysilane. Preference is given to cyclohexylmethyldimethoxysilane or diphenyldimethoxysilane.

The molar ratio of the silane compound to the titanium in the solid catalyst is 25-100:1, preferably 25-50:1.

The present invention will be described in detail below by examples, but the present invention is not limited thereto.

The test equipment, test method and conditions listed in the example are as follows:

1. Nuclear Magnetic Resonance: Use the Varian Inova 500 Hz nuclear magnetic resonance instrument of Varian Corporation of the United States to measure ¹ H-NMR [300MHz, the solvent is CDCl ₃ (deuterated chloroform), TMS (tetramethylsilane) is the internal standard, and the measurement temperature is 300K] .

2. Infrared Spectrum (IR): It was measured by the MAGNA-IR 560 infrared spectrometer of Nicolet Company, and was ground and pressed by KBr.

3. Determination method of polymer isotacticity: use Soxhlet extractor to extract with boiling n-heptane solvent for 12 hours, the percentage of insoluble part is the isotacticity of polymer.

4. Molecular weight and molecular weight distribution of the polymer: Measured by the Alliance GPCV2000 instrument of Waters Company in the United States, the test temperature is 150°C, and the solvent is 1,2,4-trichlorobenzene.

5. The magnesium and titanium contents of the solid catalyst are measured on a VISTA-AX analyzer of Varian Corporation by inductively coupled plasma emission spectrometry (ICP).

6. Determination of electron-donating compound (ID) content: Weigh a certain amount of sample and dissolve it with hydrochloric acid, extract with absolute ethanol, then add di-n-butyl phthalate (as internal standard), and make a certain volume of acidic solution . Adopt SHIMAD2U-14B gas chromatograph (chromatographic column: GDX-4012.5×3mm, FID: hydrogen flame) to measure, and operate 3295 integrator to calculate the result at the same time. The formula for calculating the internal donating electron (ID) content is as follows:

C _ID = (A _i ×W _s ×f _is )/(W _i ×A _s )

In the formula, C _ID is the content of ID; W _i is the mass of the sample; W _s is the mass of the internal standard; A _i is the integrated area of the sample ID; A _s is the integrated area of the internal standard; f _is the correction factor

7. Elemental analysis: determined by EA-1108 instrument.

Example 1

Preparation of internal electron donor compounds of formula (I) according to the present invention.

Under nitrogen atmosphere, add 24.64g (117mmol) o-hydroxybenzophenone, 250ml (2930mmol) 1,4-dioxane and 15.34g (136.7mmol) potassium tert-butoxide successively in the 500ml three-necked bottle, Stir to combine completely. React at 25°C for 1 hour, raise the temperature to 70°C for 5 hours, then add 9.45ml (186mmol) methyl iodide dropwise to the reaction liquid, and continue to react for 12 hours.

The reaction solution was filtered, and the filtrate was distilled under reduced pressure to remove the solvent and other by-products, and the remaining solution was recrystallized 5 to 6 times with hexane to obtain a white solid, which was o-methoxybenzophenone. The structural formula was as follows, and the yield was about is 83% by mass,

The ¹ H-NMR spectrum of o-methoxybenzophenone is:

IR characteristic absorption peaks are: 1243.12cm ^-1 (COC), 1625.00cm ^-1 (C=O).

Elemental analysis values, theoretical values in brackets:

C 78.86% (79.25%), H 5.68% (5.66%), O 15.41% (15.09%)

Example 2

Preparation of the internal electron donor compound of formula (II) according to the present invention.

Under a nitrogen atmosphere, 25g (80.6mmol) 2,2'-thiobis(4-methyl-6-tert-butylphenol), 250ml (2930mmol) 1,4-dioxyl Hexacyclic and 17.18g potassium tert-butoxide (153mmol), stir to make it completely mixed. React at 25°C for 1 hour, raise the temperature to 70°C for 7 hours, add 10.60 ml (209 mmol) methyl iodide dropwise to the reaction solution, and continue the reaction for 12 hours.

The reaction solution was filtered, and the filtrate was distilled under reduced pressure to remove the solvent and other by-products, and the remaining solution was recrystallized 5 to 6 times with hexane to obtain a white solid, which was 2,2'-thiobis(4-methyl-6- tert-butylanisole), structural formula is as follows, and yield is about 60 quality %,

The ¹ H-NMR spectrum of 2,2'-thiobis(4-methyl-6-tert-butylanisole) is:

IR characteristic absorption peak is: 1234.238cm ^-1 (COC).

Elemental analysis value: C 74.16% (75.00%), H 8.80% (9.00%)

Example 3

The following example prepares the solid catalyst component:

(1) Preparation of magnesium chloride spherical carrier: 33.5g of anhydrous MgCl ₂ , 80mL of absolute ethanol, 100mL of methyl silicone oil and 100mL of liquid paraffin were added to a 500mL reaction flask under the protection of N ₂ , heated to 120°C for 2 hours to make The _MgCl2 is all dissolved.

Transfer the above solution to a dispersing kettle preheated to 120°C containing 150mL of methyl silicone oil and liquid paraffin, stir at a speed of 2000 rpm, and then transfer to a precooled to -25°C containing 1000mL of hexane In the quenching kettle, stir at a speed of 500 rpm for 20 minutes, the quenched alcohol and the solidified into a spherical shape, filtered, washed the solid with hexane, and dried at 80°C to obtain a spherical carrier.

(2) Under the protection of high-purity nitrogen, add 5.7g of the magnesium chloride spherical carrier (which contains 26mmol MgCl ₂ ) prepared in step (1) into 30ml of hexane to make a suspension, and add the suspension to 120ml that has been pre-cooled to In a toluene solution containing 260 mmol of titanium tetrachloride at -10° C., the reaction was stirred at a speed of 150 rpm for 0.5 hour. Raise the temperature to 60-80°C, add 0.6g (2.8mmol) o-methoxybenzophenone prepared in Example 1 and 0.7ml (2.6mmol) diisobutyl phthalate, and react at 110°C for 2 hours. Solid particles were isolated by filtration while hot.

(3) Add the solid particles into 60 ml of toluene solution containing 130 mmol of titanium tetrachloride preheated to 110° C., react at this temperature for 1 hour, and separate the solid particles by filtration while hot. Wash away the free chloride ion on the particle with hexane at 60° C., and obtain 4.6 g of solid catalyst A after drying with nitrogen, wherein the Mg content is 19.37 mass %, the Ti content is 4.98 mass %, the ether content is 4.25 mass %, and the ester content is 6.73% by mass.

Example 4

Prepare solid catalyst component according to the method for example 3, difference is (2) adds the 2 of 0.9g (2.4mmol) in the step, 2 '-thiobis (4-methyl-6-tert-butylmethoxybenzene), The addition of magnesium chloride spherical carrier is 5.0g (containing 23mmol MgCl ₂ ), the addition of ester is 0.6ml (2.2mmol), and 4.0g of solid catalyst B is obtained, wherein the Mg content is 18.57% by mass, and the Ti content is 5.34% by mass. The ether content was 4.42% by mass, and the ester content was 6.27% by mass.

Example 5

The following examples prepare polypropylene using the catalyst of the invention.

After fully replacing the 250ml three-necked flask with nitrogen, and then fully replacing it with propylene, add 100ml of anhydrous hexane, 7.0ml of a hexane solution of triethylaluminum (AlEt ₃ ) with a concentration of 1mol/L, and 3.5ml of a concentration of A 0.1 mol/L hexane solution of diphenyldimethoxysilane (DDS) was added, and 45 mg of solid catalyst component A was added, and the temperature was raised to 45° C. for 2 hours to obtain a polypropylene resin. Catalyst A had an activity of 320 gPP/gCat, a polypropylene isotacticity of 95.6%, and a molecular weight distribution (Mw/Mn) of 7.35.

Example 6

Propylene polymerization was carried out according to the method of Example 5, except that the solid catalyst component added was 42 mg of Catalyst B, and the amounts of AlEt ₃ and DDS solution were 18.7 ml and 9.4 ml, respectively. Catalyst B had an activity of 321 gPP/gCat, a polypropylene isotacticity of 96.0%, and a molecular weight distribution (Mw/Mn) of 9.36.

Example 7

Fully replace the glass autoclave equipped with a stirring and constant temperature system with high-purity nitrogen, and then replace it three times with raw material propylene, add 400ml of anhydrous hexane under a certain positive pressure in the kettle, start stirring, and then add 5.8ml of 1 mol/L triethylaluminum hexane solution, 3.8ml concentration of 0.1 mol/L DDS hexane solution and 18.5mg solid catalyst A. Raise the temperature to 60°C, open the propylene feed valve, continue to raise the system temperature to 70°C, and control the pressure at 0.6MPa to react for 1 hour. After the reaction was over, the propylene feeding and stirring were stopped, the system was lowered to 25°C, the polymer was taken out and dried at 70°C to obtain 63.35g of polypropylene. Catalyst A had an activity of 3423 gPP/gCat, a polypropylene isotacticity of 97.2%, and a molecular weight distribution (Mw/Mn) of 5.66.

Example 8

Propylene polymerization was carried out according to the method of Example 7, but hydrogen was added to the system before the temperature was raised, and the triethylaluminum solution, DDS solution and solid catalyst A added to the system were changed to 7.2ml, 4.8ml and 23.1mg respectively, to obtain 132.24 g polypropylene. The catalyst activity was 5725 gPP/gCat, the isotacticity of polypropylene was 96.2%, and the molecular weight distribution (Mw/Mn) was 5.34.

Example 9

Carry out propylene polymerization by the method for example 7, difference is to add solid catalyst B, and the addition of AlEt ₃ and DDS solution and catalyst B is respectively 6.2ml, 4.1ml and 18.4mg, obtains 65.74g polypropylene. Catalyst B had an activity of 3573 gPP/gCat, a polypropylene isotacticity of 97.4%, and a molecular weight distribution (Mw/Mn) of 5.68.

Example 10

Propylene polymerization was carried out according to the method of Example 7, but hydrogen was added to the system before the temperature was raised, and the additions of the triethylaluminum solution and the DDS solution were changed to 10.3ml and 6.9ml respectively, and the solid catalyst added was 30.8mg catalyst B, 132.24 g of polypropylene were obtained. Catalyst B had an activity of 5924 gPP/gCat, a polypropylene isotacticity of 96.6%, and a molecular weight distribution (Mw/Mn) of 5.53.

Comparative example 1

Prepare the solid catalyst component according to the method of CN1109067A.

Prepare magnesium chloride spherical carrier according to the method of example 3 (1) step, after getting 2.0 grams of this carrier impregnated with 10ml hexane, join in the toluene solution that contains 95mmolTiCl 47ml, ₀ ℃ and react for 0.5 hour, be warming up to 80 ℃ and add 0.6 ml of diisobutyl phthalate, heated to 110°C for 2 hours. Sedimentation, filtration. The obtained solid was added to 23ml of toluene solution containing 47mmol TiCl ₄ again and reacted at 110°C for 1 hour, settled and filtered, the solid was washed 6 times with hexane, and dried at 67°C to obtain the catalyst solid component HDC.

Polypropylene was prepared according to the method of Example 5, except that the solid catalyst added was 48 mg HDC, and the amounts of AlEt ₃ and DDS solutions added were 6.1 ml and 3.1 ml, respectively, to obtain 10.6 g of polypropylene. The catalyst activity was 222gPP/gCat, the isotacticity of polypropylene was 95.7%, and the molecular weight distribution index (Mw/Mn) was 4.81.

Claims (18)

1. olefins polymerizing solid catalyst component, comprise the titanium compound and the internal electron donor that are carried on the magnesium compound carrier, Mg content is 15～25 quality % in the described catalyzer, titanium content is 1.0～10.0 quality %, internal electron donor content is 5～15 quality %, described internal electron donor comprises bialkyl ortho phthalate and is selected from formula (I) or ether compound (II) that the mass ratio of described ether and ester is 0.1～3.0: 1

Formula (I) or (II) in, R ₁Be selected from C ₁～C ₁₂Alkyl, C ₃～C ₁₂Cycloalkyl, C ₆～C ₂₀Aryl, alkaryl or aralkyl, R ₂Be the substituting group on the phenyl ring, each substituting group can be identical or different, R ₂Be selected from hydrogen, C ₁～C ₁₂Alkyl, C ₃～C ₁₂Cycloalkyl, C ₆～C ₂₀Aryl, alkaryl or aralkyl, R ₃Be selected from hydrogen, C ₁～C ₁₂Alkyl, C ₃～C ₁₂Cycloalkyl, C ₆～C ₂₀Aryl or alkaryl.

2. according to the described ingredient of solid catalyst of claim 1, it is characterized in that described R ₁Be selected from C ₁～C ₆Alkyl, phenyl or indenyl, R ₂Be selected from hydrogen or C ₁～C ₆Alkyl, R ₃Be selected from hydrogen, C ₁～C ₁₂Alkyl, phenyl or indenyl.

3. according to the described ingredient of solid catalyst of claim 1, it is characterized in that described R ₁Be selected from C ₁～C ₄Alkyl, 4,6 bit substituents are C on the phenyl ring ₁～C ₆Alkyl, 3,5 bit substituents are hydrogen, R ₃Be selected from hydrogen, C ₁～C ₆Alkyl or phenyl.

4. according to the described ingredient of solid catalyst of claim 1, it is characterized in that described R ₁Be selected from C ₁～C ₄Alkyl, 4 bit substituents are C on the phenyl ring ₁～C ₃Alkyl, 6 bit substituents be C ₃～C ₆Alkyl, 3,5 bit substituents are hydrogen, R ₃Be selected from phenyl.

5. according to the described ingredient of solid catalyst of claim 1, it is characterized in that described magnesium compound is selected from the alcohol adduct of magnesium chloride or magnesium chloride.

6. according to the described ingredient of solid catalyst of claim 1, it is characterized in that described titanium compound general formula is TiX _n(OR) _4-n, R is C in the formula ₁～C ₈Alkyl, X is a halogen, n is 1～4 integer.

7. according to the described ingredient of solid catalyst of claim 1, it is characterized in that described titanium compound is a titanium tetrachloride, the alkyl in the bialkyl ortho phthalate is C ₁～C ₆Alkyl.

8. according to the described ingredient of solid catalyst of claim 1, it is characterized in that described internal electron donor content is 5.0～15 quality %, the mass ratio of ether and ester is 0.5～1.0: 1.

9. the preparation method of the described ingredient of solid catalyst of claim 1 comprises the steps:

(1) place unreactive hydrocarbons to form suspension in the magnesium compound carrier, this suspension is joined in the compound titanium solution at 0～-20 ℃, described titanium/magnesium mol ratio is 5～60: 1, be warming up to 60～80 ℃, adding formula (I) or ether (II) and bialkyl ortho phthalate, 100～125 ℃ of fully reactions, collect solids, described magnesium/ether mol ratio is 5～25: 1, and ether/ester mol ratio is 0.5～1.7

(2) solids is added fully reaction in the compound titanium solution that is preheated to 100～125 ℃, titanium/magnesium mol ratio is 1～20: 1, removes liquid, and the solids that obtains is also dry with the unreactive hydrocarbons washing.

10. in accordance with the method for claim 9, it is characterized in that described magnesium compound carrier is spherical magnesium chloride, titanium compound is a titanium tetrachloride, and the alkyl in the bialkyl ortho phthalate is C ₁～C ₆Alkyl.

11. in accordance with the method for claim 9, it is characterized in that described unreactive hydrocarbons are hexane, heptane or straight-run spirit.

12. in accordance with the method for claim 9, the ratio that it is characterized in that unreactive hydrocarbons and magnesium compound in the described suspension of (1) step is 3.0～8.0 a milliliters/gram, and titanium/magnesium mol ratio is 5～30: 1, and titanium/magnesium mol ratio is 3～10: 1 in (2) step.

13. it is characterized in that in accordance with the method for claim 9, the solvent of compound titanium solution is toluene.

14. an olefine polymerizing process comprises that with the described solid catalyst of claim 1 be Primary Catalysts, in the presence of the promotor alkylaluminium cpd, alkene is reacted under polymerizing condition.

15. in accordance with the method for claim 14, it is characterized in that it is AlR ' that described aluminum alkyls is selected from general formula _nX _3-nCompound, R ' is hydrogen or C in the formula ₁～C ₂₀Alkyl, X is a halogen, n is 1～3 number, aluminium during reaction/titanium mol ratio is 10～500: 1.

16. in accordance with the method for claim 15, it is characterized in that described aluminum alkyls is selected from triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chlorine diisobutyl chlorine, sesquialter ethyl aluminum chloride or ethyl aluminum dichloride.

17. also add general formula when in accordance with the method for claim 14, it is characterized in that polyreaction is R ¹ _nSi (OR ²) _4-nSilane compound, 0≤n in the formula≤3, R ¹And R ²Be selected from C respectively ₁～C ₁₂Alkyl, cycloalkyl, aryl or haloalkyl.

18. it is characterized in that in accordance with the method for claim 17, the mol ratio of the titanium in described silane compound and the solid catalyst is 25～100: 1.