CN101153062B - Olefins polymerizing solid catalyst component, producing method and application of the same - Google Patents
Olefins polymerizing solid catalyst component, producing method and application of the same Download PDFInfo
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Abstract
An olefin polymerized solid catalyst component contains a titanium compound loaded on the magnesium compound and the inner electron donor. The inner electron donor comprises phthalate dialkyl ester phthalate ester and ether compounds chosen from the formula (I) or (II); the weight ratio between ether and ester is from 0.1 : 3.0 to 1. In the formula (I) or (II), R<SUB>1</SUB> is chosen from alkyl of C1 to C12, naphthene group of C3 to C12, aryl of C6 to C20, n-aryl or aryl alkyl; R2 is chosen from hydrogen, alkyl of C1 to C12, naphthene group of C3 to C12, aryl of C6-C20, n-aryl or aryl alkyl;R3 is chosen from hydrogen, alkyl of C1 to C12, naphthene group of C3 to C12, acryl or n-aryl of C6 to C20. The solid catalyst used for olefin polymerization has high activity, and the distribution of molecular weight of the prepared polyolefin is wide.
Description
Technical field
The present invention is a kind of olefins polymerizing solid catalyst component and preparation method and application, specifically, is a kind of ingredient of solid catalyst and preparation method and application in olefinic polymerization that contains the internal electron donor compound.
Background technology
CH
2=CHR olefinic polymerization, particularly having the basal component that the used ingredient of solid catalyst of alpha-olefine polymerizing of 3 carbon or more carbon atoms comprises is magnesium, titanium, halogen and electron donor compound, electron donor compound wherein is called internal electron donor more, is mainly used in to improve the polymkeric substance taxis.The internal electron donor compound of using in the prior art comprises polycarboxylic acid, monocarboxylate, multi-carboxylate, acid anhydrides, ketone, ether, alcohol or amine, and that comparatively commonly used is the multi-carboxylate.
In recent years, people attempt to adopt other compound as the electron donor in the olefins polymerizing solid catalyst component again, in CN1042547A and the described olefins polymerizing solid catalyst component of CN1143651A, the internal electron donor compound that adopts is to contain 1 of two ether groups, and the 3-diether compound is as 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal and 9,9-two (methoxymethyl) fluorenes etc.
Recently, there is report to disclose in olefin polymerization solid catalyst, use a kind of dibasic aliphatic carboxylic acid ester compound to be internal electron donor with special construction, use succinate, malonic ester, glutarate, cyano group ester and diol ester to be the internal electron donor compound as CN1313869A, CN1236373A, CN1236374A, CN1242780A, CN1453298A, CN1597714A, CN1398270A use then that two kinds of electron donor compounds are composite to be used as internal electron donor.The use of these electron donors not only can improve activity of such catalysts, and the molecular weight distribution of gained propylene polymers is obviously widened.
Olefin polymerization catalysis with the disclosed internal electron donor compound of aforesaid method, still there is certain problem in actual applications, as to adopt binary aromatic carboxylic acid's ester compound be that the activity of such catalysts of internal electron donor is lower, and the molecular weight distribution of resulting polymers is also narrower; Adopt the catalyst activity of dibasic aliphatic carboxylic acid ester compound also lower; Adopt 1, though the catalyzer of 3-diether compound is active higher, hydrogen response is also fine, and the narrow molecular weight distribution of resulting polymers is unfavorable for the exploitation of different trade mark polymeric articles.
Summary of the invention
The purpose of this invention is to provide a kind of olefins polymerizing solid catalyst component, this ingredient of solid catalyst is used for polymkeric substance degree of isotacticity height and the molecular weight distribution broad that the olefinic polymerization catalysis activity is higher and obtain.
Another object of the present invention provides the preparation method of above-mentioned catalyst component and carries out the method for olefinic polymerization with it.
Olefins polymerizing solid catalyst component provided by the invention, 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.
Electron donor in the solid catalyst of the present invention adds a kind of ethers in ester cpds commonly used, improved the polymerization activity of catalyzer, particularly in third rare polyreaction, can obtain high degree of isotacticity and than the polypropylene of wide molecular weight distribution.
Embodiment
The ethers that the present invention adopts phenols to transform is the internal electron donor compound, be used to prepare ingredient of solid catalyst with bialkyl ortho phthalate is composite, this solid catalyst is used for alkene, particularly third rare polymerization, active higher, and can obtain high degree of isotacticity, than the polypropylene of wide molecular weight distribution (Mw/Mn).
In formula provided by the invention (I) and the ether (II), R
1Group for being connected with oxygen in the phenol can be alkyl, cycloalkyl, aryl, aralkyl or alkaryl, preferred C
1～C
6Alkyl, phenyl or indenyl, more preferably C
1～C
4Alkyl.R
2Be 4 substituting groups on the phenyl ring, each substituting group can be identical or different, respectively preferred hydrogen or C
1～C
6Alkyl, comparatively preferably 4 substituting groups are hydrogen, perhaps phenyl ring 4,6 bit substituents are C
1～C
6Alkyl, 3,5 bit substituents are hydrogen; Perhaps phenyl ring 4 bit substituents are C
1～C
3Alkyl, 6 bit substituents be C
3～C
6Alkyl, 3,5 bit substituents are hydrogen.Described R
3Be the substituting group that links to each other with carbonyl in the formula (I), preferred phenyl, indenyl, C
1～C
12Alkyl or C
7～C
20Alkaryl.
Magnesium compound in the described ingredient of solid catalyst is a support of the catalyst, the alcohol adduct of preferred magnesium chloride or magnesium chloride.Titanium compound is the activity of such catalysts component, and being selected from general formula is TiX
n(OR)
4-nCompound, R is C in the formula
1～C
8Alkyl, X is a halogen, n is 1～4 integer, preferred four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, more preferably titanium tetrachloride.
Described bialkyl ortho phthalate is the another kind of electron donor in the solid catalyst, the preferred C of the alkyl in the bialkyl ortho phthalate
1～C
6Alkyl.
Preferred 5.0～15.0 quality % of the content of internal electron donor in the described ingredient of solid catalyst, the mass ratio of wherein said ether and ester preferred 0.5～1.0: 1.
The preparation method of ingredient of solid catalyst of the present invention 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.
In the described method, the preferred spherical magnesium chloride of (1) described magnesium compound carrier of step, the preferred titanium tetrachloride of titanium compound, the preferred C of the alkyl in the bialkyl ortho phthalate
1～C
6Alkyl.Unreactive hydrocarbons and preferred 3.0～8.0 milliliters of the ratio of magnesium compound/gram in the described suspension, join in the compound titanium solution after, titanium/magnesium mol ratio preferred 5～30: 1.(2) mol ratio preferred 3～10: 1 of magnesium in titanium compound that adds in the step and the carrier.
The preferred hexane of unreactive hydrocarbons in the described method, heptane or straight-run spirit.The preferred toluene of the solvent of compound titanium solution.
Described spherical magnesium chloride support can be referring to the method preparation of CN1109067A, and pure content is 1.5～4.0 moles of alcohol per mole MgCl in this carrier
2, preferred 2.0～3.0 moles of alcohol per mole MgCl
2
The ether compound that uses among the present invention can be used prepared in various methods, by corresponding phenolic compound and alkali effect, is R with excessive general formula more preferably
1The halogenated alkane reaction of X makes formula R
1Among the X, R
1Be selected from C
1～C
12Alkyl, C
3～C
12Cycloalkyl, C
6～C
20Aryl, alkaryl or aralkyl, preferred C
1～C
6Alkyl, phenyl or indenyl, more preferably C
1～C
4Alkyl, the preferred iodine of X.
In the described method with the alkoxide of the alkali preferred as alkali of phenolic compound effect, as potassium tert.-butoxide or potassium isopropoxide, the temperature of phenol and alkali reaction is 0～100 ℃, for increasing the solvability of phenolic compound, should add solvent in phenols, preferred solvent is a dioxane.Add R during reaction
1Preferred 0～100 ℃ of the temperature that X reacts, the R of adding
1The mol ratio of X and phenolic compound preferred 1.2～3.0: 1.
Olefine polymerizing process provided by the invention comprises that with solid catalyst of the present invention be Primary Catalysts, in the presence of the promotor alkylaluminium cpd, alkene is reacted under polymerizing condition.Polyreaction can be carried out in liquid phase or gas phase, also can carry out under the operation of liquid and gas polymerization stage combination.Described alkene is C
2～C
20Alpha-olefin.Suitable polymeric reaction temperature is 0～150 ℃, preferred 30～90 ℃, and pressure is 0.1～4.0MPa, preferred 0.5～3.0MPa.
Described aluminum alkyls preferred formula is AlR '
nX
3-nCompound, R ' is hydrogen or C in the formula
1～C
20Alkyl, X is a halogen, n is the number between 1～3, aluminium during reaction/titanium mol ratio is 5～1000: 1, preferred 25～500: 1.Preferred aluminum alkyls is 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.
For improving the degree of isotacticity of polymkeric substance, preferably add external electron donor during polyreaction, it is R that preferred external electron donor compound is selected from general formula
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.Preferred silane compound is trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane or methyl-t-butyldimethoxysilane.Preferred cyclohexyl methyl dimethoxy silane or dimethoxydiphenylsilane.
The mol ratio of titanium is 25～100: 1 in described silane compound and the solid catalyst, preferred 25～50: 1.
Below by example in detail the present invention, but the present invention is not limited to this.
Listed testing tool, testing method and condition are as follows in the example:
1, nucleus magnetic resonance: the 500 hertz of nmr determinations of Varian Inova that use U.S. Varian company
1H-NMR[300MHz, solvent are CDCl
3(deuterochloroform), TMS (tetramethylsilane) is interior mark, measures temperature 300K].
2, infrared spectrum (IR): adopt the MAGNA-IR 560 type determination of infrared spectroscopy of Nicolet company, adopt KBr to grind compressing tablet.
3, polymkeric substance degree of isotacticity measuring method: use Soxhlet extractor with ebullient normal heptane solvent extracting 12 hours, do not dissolve the degree of isotacticity that percentage ratio partly is polymkeric substance.
4, polymericular weight and molecular weight distribution: adopt the Alliance GPCV2000 type Instrument measuring of U.S. Waters company, probe temperature is 150 ℃, and solvent is 1,2, the 4-trichlorobenzene.
5, the magnesium of solid catalyst, titanium content adopt inductively coupled plasma emission spectrometry (ICP) to measure on the VISTA-AX of Varian company type analysis instrument.
6, give electron compound (ID) assay: take by weighing a certain amount of sample dissolving with hydrochloric acid,, add n-butyl phthalate (making internal standard substance) then, be made into the acidic solution of certain volume with the dehydrated alcohol extraction.Adopt SHIMAD2U-14B type gas chromatograph (chromatographic column: GDX-4012.5 * 3mm, FID: hydrogen flame) measure, operate 3295 totalizing instrument calculation result simultaneously.Interior electronics (ID) the cubage formula of giving is as follows:
C
ID＝(A
i×W
s×f
is)/(W
i×A
s)
C in the formula
IDBe ID content; W
iBe sample quality; W
sBe the internal standard substance quality; A
iBe sample ID integral area; A
sBe the internal standard substance integral area; f
IsBe correction factor
7, ultimate analysis: adopt EA-1108 type instrument to measure.
Example 1
The internal electron donor compound for preparing formula of the present invention (I).
Under nitrogen atmosphere, in the 500ml three-necked bottle, add 24.64g (117mmol) neighbour-dihydroxy benaophenonel, 250ml (2930mmol) 1 successively, 4-dioxane and 15.34g (136.7mmol) potassium tert.-butoxide, stirring makes it to mix fully.25 ℃ were reacted 1 hour, were warming up to 70 ℃ of reactions 5 hours, dripped 9.45ml (186mmol) methyl iodide then in reaction solution, continued reaction 12 hours.
With reacting liquid filtering, get the filtrate decompression distillation except that desolvating and other by product, surplus solution hexane recrystallization 5～6 times get white solid, are neighbour-methoxy benzophenone, and structural formula is as follows, and yield is about 83 quality %,
The O-methoxy benzophenone
1The H-NMR spectrum is:
δ3.72ppm 3H -OC
H 3
δ7.05ppm 2H
δ7.45ppm 5H
δ7.82ppm 2H
The IR charateristic avsorption band is: 1243.12cm
-1(C-O-C), 1625.00cm
-1(C=O).
In the ultimate analysis value, bracket is theoretical value:
C 78.86％(79.25％)、H 5.68％(5.66％)、O 15.41％(15.09％)
Example 2
The internal electron donor compound for preparing formula of the present invention (II).
Under nitrogen atmosphere, in the 500ml three-necked bottle, add 25g (80.6mmol) 2 successively, 2 '-thiobis (4-methyl-6-tert butyl phenol), 250ml (2930mmol) 1,4-dioxane and 17.18g potassium tert.-butoxide (153mmol) stir and make it to mix fully.25 ℃ were reacted 1 hour, were warming up to 70 ℃ of reactions 7 hours, dripped 10.60ml (209mmol) methyl iodide in reaction solution, continued reaction 12 hours.
With reacting liquid filtering, to get filtrate decompression distillation and remove and desolvate and other by product, surplus solution obtains white solid with hexane recrystallization 5～6 times, be 2,2 '-thiobis (4-methyl-6-tert butyl methyl-phenoxide), structural formula is as follows, and yield is about 60 quality %,
2,2 '-thiobis (4-methyl-6-tert butyl methyl-phenoxide)
1The H-NMR spectrum is:
δ1.40ppm 9H -C(C
H 3)
3
δ2.19ppm 6H -C
H 3
δ3.94ppm 6H -OC
H 3
δ6.75ppm 2H
δ7.02ppm 2H
The IR charateristic avsorption band is: 1234.238cm
-1(C-O-C).
Ultimate analysis value: C 74.16% (75.00%), H 8.80% (9.00%)
Example 3
Following examples preparation ingredient of solid catalyst:
(1) preparation magnesium chloride ball type carrier: with the anhydrous MgCl of 33.5g
2, 80mL dehydrated alcohol, 100mL methyl-silicone oil and 100mL whiteruss be at N
2Join in the 500mL reaction flask under the protection, be heated to 120 ℃ of reactions 2 hours, make MgCl
2All dissolvings.
Above-mentioned solution is transferred in the Scattered Kettle that methyl-silicone oil and each 150mL of whiteruss are housed that is preheated to 120 ℃, to transfer in advance in the chilling still that the 1000mL hexane is housed that is chilled to-25 ℃ after 2000 rev/mins the rotating speeds stirring, stirred 20 minutes with 500 rev/mins rotating speeds, the pure and mild thing of chilling is solidified into sphere, filter, with the solids hexane wash, 80 ℃ of dryings obtain ball type carrier.
(2) under the high pure nitrogen protection, the magnesium chloride ball type carrier that 5.7g (1) step is made (wherein contains 26mmol MgCl
2) add in the 30ml hexane and make suspension, suspension is joined 120ml be pre-chilled in-10 ℃ the toluene solution that contains the 260mmol titanium tetrachloride, with 150 rev/mins rotating speed stirring reactions 0.5 hour.Be warming up to 60～80 ℃, add the neighbour-methoxy benzophenone and 0.7ml (2.6mmol) diisobutyl phthalate of 0.6g (2.8mmol) example 1 preparation respectively, 110 ℃ were reacted 2 hours, and filtered while hot is isolated solid particulate.
(3) solid particulate is joined 60ml and be preheated in 110 ℃ the toluene solution that contains the 130mmol titanium tetrachloride, reaction is 1 hour under this temperature, and filtered while hot is isolated solid particulate.60 ℃ with free chlorion on the hexane flush away particle, and with obtaining 4.6g solid catalyst A behind the nitrogen drying, wherein Mg content is 19.37 quality %, and Ti content is 4.98 quality %, and ether content is 4.25 quality %, and ester content is 6.73 quality %.
Example 4
Method according to example 3 prepares ingredient of solid catalyst, and different is to add 2,2 of 0.9g (2.4mmol) '-thiobis (4-methyl-6-tert-butyl ylmethoxy benzene) in (2) step, and magnesium chloride ball type carrier add-on is that 5.0g (contains 23mmol MgCl
2), the add-on of ester is 0.6ml (2.2mmol), makes 4.0g solid catalyst B, wherein Mg content is 18.57 quality %, Ti content is 5.34 quality %, ether content is 4.42 quality %, ester content is 6.27 quality %.
Example 5
Following example Preparation of Catalyst polypropylene of the present invention.
After the 250ml three-necked bottle fully replaced with nitrogen, use third rare abundant displacement again, add the 100ml anhydrous hexane, 7.0ml concentration is the triethyl aluminum (AlEt of 1mol/L
3) hexane solution, the hexane solution of dimethoxydiphenylsilane (DDS) that 3.5ml concentration is 0.1mol/L, add 45mg ingredient of solid catalyst A again, be warming up to 45 ℃ of reactions 2 hours, obtain acrylic resin.The activity of catalyst A is 320gPP/gCat, and the polypropylene degree of isotacticity is 95.6%, and molecular weight distribution (Mw/Mn) is 7.35.
Example 6
Method by example 5 is carried out propylene polymerization, and different is that the ingredient of solid catalyst that adds is the 42mg catalyst B, and AlEt
3, DDS solution add-on be respectively 18.7ml and 9.4ml.The activity of catalyst B is 321gPP/gCat, and the polypropylene degree of isotacticity is 96.0%, and molecular weight distribution (Mw/Mn) is 9.36.
Example 7
Fully replace the glass autoclave that stirring and constant temperature system are housed with high pure nitrogen, use raw material third rare displacement three times again, in still, keep certain direct draught to add the 400ml anhydrous hexane, start stirring, add hexane solution and the 18.5mg solid catalyst A of hexane solution that 5.8ml concentration is the triethyl aluminum of 1mol/L, DDS that 3.8ml concentration is 0.1mol/L successively.Be warming up to 60 ℃, open third rare feed valve, continue system temperature is increased to 70 ℃, pressure-controlling was 0.6MPa reaction 1 hour.Reaction stops third rare charging and the stirring after finishing, and system is reduced to 25 ℃, takes out polymkeric substance 70 ℃ of oven dry, gets the 63.35g polypropylene.The activity of catalyst A is 3423gPP/gCat, and the polypropylene degree of isotacticity is 97.2%, and molecular weight distribution (Mw/Mn) is 5.66.
Example 8
Method by example 7 is carried out propylene polymerization, but adds hydrogen in intensification forward direction system, and changes the triethyl aluminium solution in the adding system, DDS solution and solid catalyst A into 7.2ml, 4.8ml and 23.1mg respectively, gets the 132.24g polypropylene.Catalyst activity is 5725gPP/gCat, and the polypropylene degree of isotacticity is 96.2%, and molecular weight distribution (Mw/Mn) is 5.34.
Example 9
Method by example 7 is carried out propylene polymerization, and different is to add solid catalyst B, and AlEt
3Be respectively 6.2ml, 4.1ml and 18.4mg with the add-on of DDS solution and catalyst B, get the 65.74g polypropylene.The activity of catalyst B is 3573gPP/gCat, and the polypropylene degree of isotacticity is 97.4%, and molecular weight distribution (Mw/Mn) is 5.68.
Example 10
Method by example 7 is carried out propylene polymerization, but adds hydrogen in intensification forward direction system, and changes triethyl aluminium solution and DDS solution add-on into 10.3ml, 6.9ml respectively, and the solid catalyst of adding is the 30.8mg catalyst B, gets the 132.24g polypropylene.The activity of catalyst B is 5924gPP/gCat, and the polypropylene degree of isotacticity is 96.6%, and molecular weight distribution (Mw/Mn) is 5.53.
Comparative Examples 1
Method by CN1109067A prepares ingredient of solid catalyst.
Method by example 3 (1) step prepares the magnesium chloride ball type carrier, get 2.0 these carriers of gram with 10ml hexane dipping after, join 47ml, 0 ℃ contain 95mmol TiCl
4Toluene solution in reaction 0.5 hour, be warming up to 80 ℃ and add the 0.6ml diisobutyl phthalates, be warming up to 110 ℃ of reactions 2 hours.Sedimentation is filtered.The gained solid adds 23ml once more and contains 47mmolTiCl
4Toluene solution in 110 ℃ of reactions 1 hour, sedimentation, filtration, solid obtains catalyst solid constituent HDC with hexane wash 6 times after 67 ℃ of dryings.
Press the preparation polypropylene of the method for example 5, different is that the solid catalyst that adds is 48mg HDC, AlEt
3, DDS solution add-on be respectively 6.1ml, 3.1ml, make the 10.6g polypropylene.Catalyst activity is 222gPP/gCat, and the polypropylene degree of isotacticity is 95.7%, and molecular weight distributing index (Mw/Mn) is 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 phenyl.
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.
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.
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.
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 ingredient of 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 ingredient of solid catalyst is 25～100: 1.
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| CN1199056A (en) * | 1997-05-13 | 1998-11-18 | 中国石油化工总公司 | Carried polypropylene catalyst |
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