CN101643520A - Catalyst for propene polymerization - Google Patents
Catalyst for propene polymerization Download PDFInfo
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- CN101643520A CN101643520A CN200810117895A CN200810117895A CN101643520A CN 101643520 A CN101643520 A CN 101643520A CN 200810117895 A CN200810117895 A CN 200810117895A CN 200810117895 A CN200810117895 A CN 200810117895A CN 101643520 A CN101643520 A CN 101643520A
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Abstract
The invention provides a catalyst for propene polymerization, which comprises the following components: A, a titanium-containing solid catalyst component, B, an alkylaluminium compound, and C, an organosilicone compound; and the invention also provides a method for preparing the titanium-containing solid catalyst component A. The titanium-containing solid catalyst component comprises titanium, magnesium, halogen, a surface modifier and a polyol ester compound with a special structure, or the polyol ester compound with the special structure which is taken as an electron doner and an electron doner compound with another structure are reasonably compatible with each other and are used in a catalyst system which is modified by the surface modifier to prepare a catalyst component and a catalystwith better comprehensive performance. Particularly, the catalyst provided by the invention shows high polymerization activity and stereospecificity when used for olefin polymerization, in particularthe propene polymerization; and simultaneously, the prepared polymer has wide molecular weight distribution and more facilitates the processing and application.
Description
Technical field
The present invention relates to a kind of olefin polymerization catalysis that is used for, the particularly a kind of catalyzer of propylene polymerization and preparation method of titanium-containing catalyst solid ingredient of being used for.
Background technology
Containing the titanium compound that loads on the magnesium halide in active and the catalyzer of electron donor compound is well known in the prior art.
U.S. Pat 4544717 discloses, and by add the electron donor compound in the solid ingredient that contains titanium compound, can improve the stereospecificity of catalyzer.Up to now, existing many patent disclosures the multiple internal electron donor compound that is applicable to the preparation Ziegler-Natta catalyst, and the olefin polymerization catalysis that comprises these internal electron donor compounds.
These internal electron donor compounds comprise: the electron donor compound of the described phthalate of EP0045977, EP0361493, describe among the EP0728724 1, the 3-diether compound, describe among the CN1105671A 1, the 3-cyclohexadione compounds, CN1236732, CN1236733, CN1236734, the malonic ester compounds of the special replacement of describing among the CN1292800, the succinate compounds of describing among the PCT W00063261, the beta substitution glutarate compounds of describing among the PCT W00055215, the cyano group ester compound of describing among the CN1242780, the two amine electron donor compounds of describing among the CN1087918, the electron donor compound of the maleic acid ester class of describing among the PCTW003022894, and CN1436766A, the polyol ester compounds of describing among the CN1436796A etc.
Disclose a kind of polyol ester compounds (A) at CN1436766, this compound is suitable for the Preparation of catalysts of olefinic polymerization very much.All having described with this special polynary ester compound (A) among CN1436796A, the CN1453298A is catalyst component that is used for olefinic polymerization and the catalyzer that internal electron donor obtains, and point out that compound (A) can be used for preparing catalyzer with compound the making of other electron donor compound, but the result of the embodiment that from patent, provides, this compound (A) is not very good with the performance of the catalyzer that the other compound use of electron donor obtains, and particularly the polymerization activity of catalyzer and hydrogen regulation performance also do not make us very satisfied.
CN1718594A discloses a kind of catalyst system that is used for olefinic polymerization, by magnesium halide being dissolved in organic epoxy compounds, organo phosphorous compounds and the inert diluent, form homogeneous solution, halogenide or derivatives thereof with titanium in the presence of precipitation additive is separated out the precipitation of solid material that contains magnesium/titanium, on this titanium/magnesium solids, further at least a coating materials in the load again, the halogenide or derivatives thereof of at least a transition metals Ti and at least a electron donor(ED) and obtain; The particle form of this catalyzer, stereospecificity and the performance of anti-impurity ability are better, but also do not make us very satisfied on the molecular weight distribution of catalyzer.
The inventor finds can to prepare more good catalyst component of over-all properties and catalyzer by selecting for use a kind of polyol ester compound with special construction as electron donor(ED) or select for use polyol ester compound with special construction to be used for the catalyst system that existing coating materials was handled as the electron donor(ED) and the electronic donor compound capable reasonable compatibility of structure in addition.It is worthy of note that catalyzer of the present invention is being used for olefinic polymerization, is particularly showing very high polymerization activity and stereospecificity during propylene polymerization, the molecular weight distribution broad of resulting polymers is more conducive to processed and applied simultaneously.
Summary of the invention
A kind of catalyzer that is used for propylene polymerization of the present invention comprises following component:
A, titaniferous ingredient of solid catalyst, it is the solvent system formation homogeneous solution that is dissolved in organic epoxy compounds, organo phosphorous compounds by magnesium halide, in the presence of precipitation additive, the halogenide or derivatives thereof that adds transition metals Ti, and handle with electronic donor compound capable 1, separate out the precipitation of solid material that contains magnesium/titanium, at at least a coating materials in the load again on this precipitation of solid material, the halogenide or derivatives thereof of at least a transition metals Ti, with electronic donor compound capable D, with obtaining after the thinner washing; Wherein said electronic donor compound capable 1 is selected from the binary alcohol esters compounds shown in the general formula (I):
R in the formula
1-R
6, R
1-R
2nGroup is identical or different hydrogen, halogen or the replacement or the C of unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene or C
10-C
20Fused ring aryl; But R
1And R
2Not hydrogen, R
3-R
6And R
1-R
2nComprise one or several heteroatoms on the group arbitrarily as carbon or hydrogen atom or both substituents, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R
3-R
6And R
1-R
2nOne or more in the group at random link up into ring or Cheng Huan not; N is the integer of 0-10;
Described electron donor compound is disclosed among Chinese patent CN1436766 and the CN1436796A, and the associated viscera of this patent disclosure is all introduced the present invention as a reference.
In the binary alcohol esters compounds shown in the above-mentioned general formula (I), the compound shown in the preferred formula (II).
R in the formula
1～R
6C for identical or different hydrogen, halogen or replacement or unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene or C
10-C
20Fused ring aryl; But R
1And R
2Not hydrogen, R
3-R
6And R
1-R
2Comprise one or several heteroatoms on the group arbitrarily as carbon or hydrogen atom or both substituents, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R
3-R
6And R
1-R
2One or more in the group at random link up into ring or Cheng Huan not; Concrete as 2,4-pentanediol dibenzoate, 4-ethyl-3,5 heptanediol dibenzoate etc.
Magnesium halide described in the catalyst component A of the present invention is a magnesium dihalide, the complex compound of the water of magnesium dihalide and alcohol, a kind of by in alkyl or the-oxyl institute metathetical derivative of one of them halogen atom in the magnesium dihalide molecular formula, or their mixture.Above-mentioned magnesium dihalide is specially: magnesium dichloride, dibrominated magnesium, two magnesium iodides, preferred magnesium dichloride.
Organic epoxy compounds described in the catalyst A component of the present invention is selected from and comprises the compounds such as oxide compound, glycidyl ether and inner ether of carbonatoms at 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine.Concrete as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether etc.
Organo phosphorous compounds described in the catalyst A component of the present invention is selected from the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, for example: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, phosphorous acid benzene methyl etc.
Precipitation additive described in the catalyst A component of the present invention is selected from a kind of in organic acid, organic acid anhydride, ether, the ketone or their mixture.Concrete as: diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether etc., preferred Tetra hydro Phthalic anhydride.
The used alcohol of coating materials is the straight chain alcohol or the isomery alcohol of 1～8 carbon atom among the catalyst component A of the present invention, for example: a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, octanol, the isooctyl alcohol, or their mixture.
The used ether of coating materials is lower aliphatic ether among the catalyst component A of the present invention, and the lower aliphatic ether of replacement is specially methyl ether, ether, propyl ether, butyl ether, ethyl isobutyl ether, amyl ether, isoamyl oxide, phenyl ethyl ether, tetrahydrofuran (THF) etc.
Electronic donor compound capable D can be identical with above-mentioned electronic donor compound capable 1 among the catalyst component A of the present invention, be the binary alcohol esters compounds shown in the binary alcohol esters compounds shown in the general formula (I), the preferred formula (II), with 2,4-pentanediol dibenzoate, 4-ethyl-3,5 heptanediol dibenzoate is good.Electronic donor compound capable D also comprises alkyl ester, aliphatic ether, cyclic aliphatic ether or the aliphatic ketone of aliphatic series and aromatic monocarboxylate's alkyl ester, aliphatic series and aromatic polycarboxylic acid among the catalyst component A of the present invention.Comprise C
1～C
4The alkyl ester of aliphatic saturated monocarboxylic acid, C
7～C
8The alkyl ester of aromatic carboxylic acid, C
2～C
6Aliphatic ether, C
3～C
4Cyclic ethers or C
3～C
6Saturated fatty ketone.The alkyl ester of preferred aromatic polycarboxylic acid, with diisobutyl phthalate, n-butyl phthalate is good.
The general formula of the compound of the transition metals Ti described in the catalyst component A of the present invention is Ti (OR)
4-nX
n, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen atom, n is 0 to 4 integer, specifically can select a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium or their mixture for use, preferred titanium tetrachloride.
Inert diluent described in the catalyst component A of the present invention can adopt a kind of or their mixture in hexane, heptane, octane, decane, the benzene,toluene,xylene.
Amount ratio between described each component of catalyst component A of the present invention is in every mole of magnesium halide, 0.2～10 mole of organic epoxy compounds, with 0.5～4 mole for well; 0.1～3 mole of organo phosphorous compounds, with 0.3～1 mole for well; 0.03～1 mole of precipitation additive, with 0.05～0.4 mole for well; 0.005～15 mole of coating materials, with 0.06～10 mole for well; 0.5～20 mole of the compound of transition metals Ti, with 1～15 mole for well; Electronic donor compound capable is 0.005～15 mole, with 0.06～10 mole for well.B, alkylaluminium cpd, its general formula are AlR
nX
3-n, in the formula R can for hydrogen, and carbonatoms be 1～20 alkyl, particularly alkyl, aralkyl, aryl; X is halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.Particular compound is as aluminum alkyl halides such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, two different aluminium triethyl, wherein with triethyl aluminum, triisobutyl aluminium for well.
In the catalyst system of the present invention, in the B component among aluminium and the component A mol ratio of titanium be 5～5000, be preferably 20～500.
C, silicoorganic compound, its general formula are R
n 1R
2 mSi (OR ')
4-n-m, R in the formula
1, R
2Identical or different, be C
1～C
20Alkyl, cycloalkyl or aryl, R ' is for containing the alkyl of 1～4 carbon atom, n, m are respectively 0～3 integer, but will satisfy the integer that n+m equals 1,2 or 3; Concrete as: the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methylcyclohexyl diethoxy silane, methylcyclohexyl dimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane etc.Ratio between B component and the component C counts 5～30 with aluminium and silicon mol ratio.
The preparation method who is used for the catalyst component A of propylene polymerization of the present invention under agitation is dissolved in magnesium halide organic epoxy compounds for (1), form homogeneous solution in organo phosphorous compounds and the inert diluent, in the presence of precipitation additive, under-30～60 ℃ of temperature, be preferably in-30～5 ℃, titanium compound is splashed into above-mentioned magnesium halide homogeneous solution or the magnesium halide homogeneous solution is splashed in the titanium compound, reaction mixture is warming up to 60～110 ℃ again, add electron donor(ED) 1, suspension was stirred under this temperature 0.5～8 hour, the elimination mother liquor obtains containing the solids of magnesium/titanium after inert diluent washing.(2) above-mentioned solids is suspended in the inert diluent, under-30～50 ℃ of temperature, add the halogenide or derivatives thereof of coating materials and transition metals Ti, under agitation be warming up in 10～80 ℃ of scopes, add electron donor(ED) D, under 100～130 ℃ of temperature, continue reaction 0.5～8 hour, leach liquid, use the mixture process 1～2 time of the halogenide of transition metals Ti and inert diluent again, leach liquid, wash solids with inert diluent, make titaniferous ingredient of solid catalyst.
The inventor finds can to prepare more good catalyst component of over-all properties and catalyzer by selecting for use a kind of polyol ester compound with special construction as electron donor(ED) or select for use polyol ester compound with special construction to be used for the catalyst system that existing coating materials was handled as the electron donor(ED) and the electronic donor compound capable reasonable compatibility of structure in addition.Catalyzer of the present invention is being used for olefinic polymerization, is particularly showing very high polymerization activity and stereospecificity during propylene polymerization, the molecular weight distribution broad of resulting polymers simultaneously, and the polymer beads form is good, is more conducive to processed and applied.
Embodiment
Provide following examples so that the present invention is described better rather than restriction the present invention.
The propylene polymerization step:
In 5 liters of autoclaves, adopt stream of nitrogen gas under 70 ℃, to blow row 1 hour, at room temperature introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, hexane solution (concentration of CHMMS is 0.11mmol/ml), 10ml anhydrous hexane and the 10mg ingredient of solid catalyst of 1ml cyclohexyl methyl dimethoxy silane (CHMMS) in the stream of nitrogen gas then.Close autoclave, introduce the hydrogen of 1.5NL and the liquid propene of 1.5Kg; In under agitation 10 minutes temperature is risen to 70 ℃., stop stirring after 2 hours 70 ℃ of following polyreactions, remove unpolymerized propylene monomer, collected polymer 70 ℃ of following vacuum-dryings 1 hour, is weighed and is calculated catalyst activity (AC); Measure the degree of isotacticity (II) of polymkeric substance with the boiling n-heptane extraction process, measure the melting index (MI) of polymkeric substance by testing standard GB/T3682-2000, it is the mensuration (standard specimen: PS of solvent under 150 ℃ with the trichlorobenzene that molecular weight distribution MWD (MWD=Mw/Mn) adopts PL-GPC220, flow velocity: 1.O ml/min, pillar: 3xPlgel 10urn MlxED-B300x7.5nm).
Embodiment 1
Repeating in the metathetical reactor through high pure nitrogen, add 6.5 kilograms of Magnesium Chloride Anhydrouss successively, 132.7 rise toluene, 5.4 rise epoxy chloropropane, 16.9 rise tributyl phosphate, at mixing speed 130rpm, temperature is under 60 ℃ the condition, reacted 2.5 hours, add the 1.89Kg phthalic anhydride then, continue reaction one hour, be cooled to-28 ℃, drip 75.8 liters of titanium tetrachlorides, be warming up to 75 ℃ gradually, slowly add 2.2mol 2,4-pentanediol dibenzoate is warming up to 85 ℃ gradually, constant temperature one hour, the elimination mother liquor repeatedly washs after drying through inert diluent toluene and organic solvent hexane, obtains containing the solids of magnesium/titanium.
The solids that contains magnesium/titanium that obtains is suspended in the toluene, adds 1.4 liters of ethanol and 64 liters of titanium tetrachlorides, under agitation be warming up to 110 ℃ gradually at-10 ℃, add 4.4mol 2 again, 4-pentanediol dibenzoate is then 110 ℃ of following constant temperature 1 hour, behind the filtering liquid, add 52 liters of titanium tetrachlorides, 78 liters of toluene solutions, 110 ℃ of constant temperature 2 hours, re-treatment was once again after the filtration, use hexane wash then 5 times, the remaining solid product obtains solid titanium catalyst component A through vacuum-drying.
Embodiment 2
Repeat in the metathetical reactor through high pure nitrogen, add 6.5 kilograms of Magnesium Chloride Anhydrouss successively, 132.7 rise toluene, 5.4 rise epoxy chloropropane, 16.9 rise tributyl phosphate, at mixing speed 130rpm, temperature is under 60 ℃ the condition, reacted 2.5 hours, add the 1.89Kg phthalic anhydride then, continue reaction one hour, be cooled to-28 ℃, drip 75.8 liters of titanium tetrachlorides, be warming up to 75 ℃ gradually, slowly add 3.3mol 2,4-pentanediol dibenzoate is warming up to 85 ℃ gradually, constant temperature one hour, the elimination mother liquor repeatedly washs after drying through inert diluent toluene and organic solvent hexane, obtains containing the solids of magnesium/titanium.
The solids that will contain magnesium/titanium is suspended in the toluene, adds 1.4 liters of ethanol and 64 liters of titanium tetrachlorides at-10 ℃, under agitation is warming up to 110 ℃ gradually, add 3.3mol 2 again, 4-pentanediol dibenzoate is then 110 ℃ of following constant temperature 1 hour, behind the filtering liquid, add 52 liters of titanium tetrachlorides, 78 liters of toluene solutions, 110 ℃ of constant temperature 2 hours, re-treatment was once again after the filtration, use hexane wash then 5 times, the remaining solid product obtains solid titanium catalyst component A through vacuum-drying.
Embodiment 3
Repeat in the metathetical reactor through high pure nitrogen, add 6.5 kilograms of Magnesium Chloride Anhydrouss successively, 132.7 rise toluene, 5.4 rise epoxy chloropropane, 16.9 rise tributyl phosphate, at mixing speed 130rpm, temperature is under 60 ℃ the condition, reacted 2.5 hours, add the 1.89Kg phthalic anhydride then, continue reaction one hour, be cooled to-28 ℃, drip 75.8 liters of titanium tetrachlorides, be warming up to 75 ℃ gradually, slowly add 4.4mol 2,4-pentanediol dibenzoate is warming up to 85 ℃ gradually, constant temperature one hour, the elimination mother liquor repeatedly washs after drying through inert diluent toluene and organic solvent hexane, obtains containing the solids of magnesium/titanium.
The solids that will contain magnesium/titanium is suspended in the toluene, adds 1.4 liters of ethanol and 64 liters of titanium tetrachlorides at-10 ℃, under agitation is warming up to 110 ℃ gradually, add 2.2mol 2 again, 4-pentanediol dibenzoate is then 110 ℃ of following constant temperature 1 hour, behind the filtering liquid, add 52 liters of titanium tetrachlorides, 78 liters of toluene solutions, 110 ℃ of constant temperature 2 hours, re-treatment was once again after the filtration, use hexane wash then 5 times, the remaining solid product obtains solid titanium catalyst component A through vacuum-drying.
Embodiment 4
With among the embodiment 12,4-pentanediol dibenzoate is changed to 4-ethyl-3, the 5 heptanediol dibenzoate of 1.2 times of molar weights.
Embodiment 5
With among the embodiment 22,4-pentanediol dibenzoate is changed to 4-ethyl-3, the 5 heptanediol dibenzoate of 1.2 times of molar weights.
Embodiment 6
With among the embodiment 32,4-pentanediol dibenzoate is changed to 4-ethyl-3, the 5 heptanediol dibenzoate of 1.2 times of molar weights.
Comparative example 1
Repeating in the metathetical reactor through high pure nitrogen, add 6.5 kilograms of Magnesium Chloride Anhydrouss, 132.7 liters of toluene, 5.4 liters of epoxy chloropropane, 16.9 liters of tributyl phosphates successively, be under 60 ℃ the condition in mixing speed 130rpm, temperature, reacted 2.5 hours, add the 1.89Kg phthalic anhydride then, continue reaction one hour, be cooled to-28 ℃, drip 75.8 liters of titanium tetrachlorides, be warming up to 85 ℃ gradually, constant temperature one hour, elimination mother liquor, repeatedly wash after drying through inert diluent toluene and organic solvent hexane, obtain containing the solids of magnesium/titanium.
The solids that will contain magnesium/titanium is suspended in the toluene, add 1.4 liters of ethanol and 64 liters of titanium tetrachlorides at-10 ℃, under agitation be warming up to 110 ℃ gradually, add the 5mol diisobutyl phthalate again, then 110 ℃ of following constant temperature 1 hour, behind the filtering liquid, add 52 liters of titanium tetrachlorides, 78 liters of toluene solutions, 110 ℃ of constant temperature 2 hours, after the filtration again re-treatment once use hexane wash then 5 times, the remaining solid product obtains solid titanium catalyst component A through vacuum-drying.
Comparative example 2
Repeating in the metathetical reactor through high pure nitrogen, add 6.5 kilograms of Magnesium Chloride Anhydrouss successively, 130 liters of toluene, 5.4 rise epoxy chloropropane, 16.9 rise tributyl phosphate, at mixing speed 130rpm, temperature is under 60 ℃ the condition, reacted 2.5 hours, add the 1.89Kg phthalic anhydride then, continue reaction one hour, be cooled to-28 ℃, drip 75.8 liters of titanium tetrachlorides, heat up gradually, add 6.5mol 2,4-pentanediol dibenzoate is warming up to 85 ℃, constant temperature one hour, the elimination mother liquor repeatedly washs after drying through inert diluent toluene and organic solvent hexane, obtains containing the solids of magnesium/titanium.
The solids that will contain magnesium/titanium is suspended in 81 liters of toluene, adds 54 liters of titanium tetrachlorides, 110 ℃ of constant temperature 2 hours, after the filtration again re-treatment once use hexane wash then 5 times, the remaining solid product obtains solid titanium catalyst component through vacuum-drying.
Comparative example 3
With 6.5mol 2 in the comparative example 2,4-pentanediol dibenzoate is changed to 7.0mol 4-ethyl-3,5 heptanediol dibenzoate.
Embodiment 7
Repeating in the metathetical reactor through high pure nitrogen, add 6.5 kilograms of Magnesium Chloride Anhydrouss successively, 132.7 rise toluene, 5.4 rise epoxy chloropropane, 16.9 rise tributyl phosphate, at mixing speed 130rpm, temperature is under 60 ℃ the condition, reacted 2.5 hours, add the 1.89Kg phthalic anhydride then, continue reaction one hour, be cooled to-28 ℃, drip 75.8 liters of titanium tetrachlorides, be warming up to 75 ℃ gradually, slowly add 2.2mol 2,4-pentanediol dibenzoate is warming up to 85 ℃ gradually, constant temperature one hour, the elimination mother liquor repeatedly washs after drying through inert diluent toluene and hexane, obtains containing the solids of magnesium/titanium.
The solids that will contain magnesium/titanium is suspended in the toluene, add 1.4 liters of ethanol and 64 liters of titanium tetrachlorides at-10 ℃, under agitation be warming up to 110 ℃ gradually, add the 4.4mol diisobutyl phthalate again, then 110 ℃ of following constant temperature 1 hour, behind the filtering liquid, add 52 liters of titanium tetrachlorides, 78 liters of toluene solutions, 110 ℃ of constant temperature 2 hours, after the filtration again re-treatment once use hexane wash then 5 times, the remaining solid product obtains solid titanium catalyst component A through vacuum-drying.
Embodiment 8
Repeat in the metathetical reactor through high pure nitrogen, add 6.5 kilograms of Magnesium Chloride Anhydrouss successively, 132.7 rise toluene, 5.4 rise epoxy chloropropane, 16.9 rise tributyl phosphate, at mixing speed 130rpm, temperature is under 60 ℃ the condition, reacted 2.5 hours, add the 1.89Kg phthalic anhydride then, continue reaction one hour, be cooled to-28 ℃, drip 75.8 liters of titanium tetrachlorides, be warming up to 75 ℃ gradually, slowly add 3.3mol 2,4-pentanediol dibenzoate is warming up to 85 ℃ gradually, constant temperature one hour, the elimination mother liquor repeatedly washs after drying through inert diluent toluene and hexane, obtains containing the solids of magnesium/titanium.
The solids that will contain magnesium/titanium is suspended in the toluene, add 1.4 liters of ethanol and 64 liters of titanium tetrachlorides at-10 ℃, under agitation be warming up to 110 ℃ gradually, add the 3.3mol diisobutyl phthalate again, then 110 ℃ of following constant temperature 1 hour, behind the filtering liquid, add 52 liters of titanium tetrachlorides, 78 liters of toluene solutions, 110 ℃ of constant temperature 2 hours, after the filtration again re-treatment once use hexane wash then 5 times, the remaining solid product obtains solid titanium catalyst component through vacuum-drying.
Embodiment 9
Repeat in the metathetical reactor through high pure nitrogen, add 6.5 kilograms of Magnesium Chloride Anhydrouss successively, 132.7 rise toluene, 5.4 rise epoxy chloropropane, 16.9 rise tributyl phosphate, at mixing speed 130rpm, temperature is under 60 ℃ the condition, reacted 2.5 hours, add the 1.89Kg phthalic anhydride then, continue reaction one hour, be cooled to-28 ℃, drip 75.8 liters of titanium tetrachlorides, be warming up to 75 ℃ gradually, slowly add 4.4mol 2,4-pentanediol dibenzoate is warming up to 85 ℃ gradually, constant temperature one hour, the elimination mother liquor repeatedly washs after drying through inert diluent toluene and hexane, obtains containing the solids of magnesium/titanium.
The solids that will contain magnesium/titanium is suspended in the toluene, add 1.4 liters of ethanol and 64 liters of titanium tetrachlorides at-10 ℃, under agitation be warming up to 110 ℃ gradually, add the 2.2mol diisobutyl phthalate again, then 110 ℃ of following constant temperature 1 hour, behind the filtering liquid, add 52 liters of titanium tetrachlorides, 78 liters of toluene solutions, 110 ℃ of constant temperature 2 hours, after the filtration again re-treatment once use hexane wash then 5 times, the remaining solid product obtains solid titanium catalyst component A through vacuum-drying.
Embodiment 10
Among the embodiment 12,4-pentanediol dibenzoate is changed to 4-ethyl-3, the 5 heptanediol dibenzoate of 1.2 times of molar weights.
Embodiment 11
Among the embodiment 22,4-pentanediol dibenzoate is changed to 4-ethyl-3, the 5 heptanediol dibenzoate of 1.2 times of molar weights.
Embodiment 12
Among the embodiment 32,4-pentanediol dibenzoate is changed to 4-ethyl-3, the 5 heptanediol dibenzoate of 1.2 times of molar weights.
The contrast of table 1 experimental result
From the data of table 1 embodiment and Comparative Examples more as can be seen, at least a coating materials in titanium/magnesium solids load in the present invention, after front and back add binary alcohol esters compounds electron donor for twice, the molecular weight distribution of polymkeric substance also has obviously and widens when keeping high activity of catalyst, and the catalyzer that obtains has had bigger improvement aspect over-all properties.
The contrast of table 2 experimental result
From the data of table 2 embodiment and Comparative Examples more as can be seen, at least a coating materials in titanium/magnesium solids load in the present invention, after front and back add the alkyl ester electron donor of binary alcohol esters compounds and aromatic polycarboxylic acid respectively, the catalyzer that obtains all has bigger improvement at aspects such as activity, degree of isotacticity, molecular weight distribution, and over-all properties obviously improves.
Claims (11)
1, a kind of allyl polymeric catalyzer that is used for is characterized in that, comprises following component:
A, titaniferous ingredient of solid catalyst, it is the solvent system formation homogeneous solution that is dissolved in organic epoxy compounds, organo phosphorous compounds by magnesium halide, in the presence of precipitation additive, the halogenide or derivatives thereof that adds transition metals Ti, and handle with electronic donor compound capable 1, separate out the precipitation of solid material that contains magnesium/titanium, at at least a coating materials in the load again on this precipitation of solid material, the halogenide or derivatives thereof of at least a transition metals Ti, with electronic donor compound capable D, with obtaining after the thinner washing; Wherein said electronic donor compound capable 1 is selected from the binary alcohol esters compounds shown in the general formula (I):
R in the formula
1-R
6, R
1-R
2nGroup is identical or different hydrogen, halogen or the replacement or the C of unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene or C
10-C
20Fused ring aryl; But R
1And R
2Not hydrogen, R
3-R
6And R
1-R
2nComprise one or several heteroatoms on the group arbitrarily as carbon or hydrogen atom or both substituents, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R
3-R
6And R
1-R
2nOne or more in the group at random link up into ring or Cheng Huan not; N is the integer of 0-10;
Coating materials is alcohol, a kind of in the ether or their mixture, and precipitation additive is organic acid anhydride, organic acid, ether or ketone;
Electronic donor compound capable D is alkyl ester, aliphatic ether, cyclic aliphatic ether or the aliphatic ketone of alkyl ester, aliphatic series and the aromatic polycarboxylic acid of binary alcohol esters compounds, aliphatic series and the aromatic monocarboxylate shown in the general formula (I);
B, alkylaluminium cpd, its general formula are AlR
nX
3-n, in the formula R be hydrogen, and carbonatoms be 1～20 alkyl, X is a halogen, n is the integer of 0＜n≤3, the ratio between B component and the component A is 5～5000 with aluminium and titanium molar ratio computing;
C, silicoorganic compound, its general formula are R
n 1R
2 mSi (OR ')
4-n-m, R in the formula
1, R
2Identical or different, be C
1～C
20Alkyl, cycloalkyl or aryl, R ' is for containing the alkyl of 1～4 carbon atom, n, m are respectively 0～3 integer, equal 1,2 or 3 but will satisfy n+m; Ratio between B component and the component C counts 5～30 with aluminium and silicon mol ratio.
2, the catalyzer that is used for propylene polymerization according to claim 1 is characterized in that, electronic donor compound capable 1 is selected from the binary alcohol esters compounds shown in the general formula (II) in the A component:
R in the formula
1～R
6C for identical or different hydrogen, halogen or replacement or unsubstituted straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20Aralkyl, C
2-C
10Alkylene or C
10-C
20Fused ring aryl; But R
1And R
2Not hydrogen, R
3-R
6And R
1-R
2Comprise one or several heteroatoms on the group arbitrarily as carbon or hydrogen atom or both substituents, described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R
3-R
6And R
1-R
2One or more in the group at random link up into ring or Cheng Huan not.
3, the catalyzer that is used for propylene polymerization according to claim 1 is characterized in that, precipitation additive is a Tetra hydro Phthalic anhydride in the A component.
4, the catalyzer that is used for propylene polymerization according to claim 1 is characterized in that, coating materials is the straight chain alcohol or the isomery alcohol of 1～8 carbon atom in the A component, and ether is lower aliphatic ether, the lower aliphatic ether of replacement.
5, the catalyzer that is used for propylene polymerization according to claim 4 is characterized in that, coating materials is a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, octanol, the isooctyl alcohol in the A component, or their mixture.
6, the catalyzer that is used for propylene polymerization according to claim 4 is characterized in that, coating materials is a kind of of methyl ether, ether, propyl ether, butyl ether, amyl ether in the A component, or their mixture.
7, the catalyzer that is used for propylene polymerization according to claim 1 is characterized in that, electronic donor compound capable D is the binary alcohol esters compounds shown in the general formula (II) or the alkyl ester of aromatic polycarboxylic acid in the A component.
8, the catalyzer that is used for propylene polymerization according to claim 7, it is characterized in that, electronic donor compound capable D is 2 in the A component, 4-pentanediol dibenzoate, 4-ethyl-3,5 heptanediol dibenzoate, diisobutyl phthalate or n-butyl phthalate.
9, any one described preparation method who is used for the catalyst component A of propylene polymerization is in the claim 1～8:
(1) under agitation magnesium halide is dissolved in organic epoxy compounds, organo phosphorous compounds and the inert diluent and forms homogeneous solution, in the presence of precipitation additive, under-30～60 ℃ of temperature, titanium compound is splashed into above-mentioned magnesium halide homogeneous solution or the magnesium halide homogeneous solution is splashed in the titanium compound, reaction mixture is warming up to 60～110 ℃ again, add electron donor(ED) 1, suspension was stirred under this temperature 0.5～8 hour, the elimination mother liquor obtains containing the solids of magnesium/titanium after inert diluent washing;
(2) above-mentioned solids is suspended in the inert diluent, under-30～50 ℃ of temperature, add the halogenide or derivatives thereof of coating materials and transition metals Ti, under agitation be warming up in 10～80 ℃ of scopes, add electron donor(ED) D, under 100～130 ℃ of temperature, continue reaction 0.5～8 hour, leach liquid, use the mixture process 1～2 time of the halogenide of transition metals Ti and inert diluent again, leach liquid, wash solids with inert diluent, make titaniferous ingredient of solid catalyst.
10, the preparation method who is used for the catalyst component A of propylene polymerization according to claim 9, it is characterized in that, preparation method (1) under agitation is dissolved in magnesium halide in organic epoxy compounds, organo phosphorous compounds and the inert diluent and forms homogeneous solution, in the presence of precipitation additive, the cooling scope is-30～5 ℃.
11, any one described application that is used for the catalyzer of propylene polymerization at propylene polymerization of claim 1～8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810117895 CN101643520B (en) | 2008-08-07 | 2008-08-07 | Catalyst for propene polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810117895 CN101643520B (en) | 2008-08-07 | 2008-08-07 | Catalyst for propene polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101643520A true CN101643520A (en) | 2010-02-10 |
| CN101643520B CN101643520B (en) | 2011-11-02 |
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ID=41655600
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102286118A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Titanium-containing solid catalyst component and catalyst for polymerization of olefin |
| CN102464733A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method thereof as well as olefin polymerization method |
| CN102838696A (en) * | 2011-06-24 | 2012-12-26 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, olefin polymerization method and applications |
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| CN114456289A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization, and preparation method and application thereof |
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| US20030022786A1 (en) * | 2001-05-03 | 2003-01-30 | Epstein Ronald A. | Catalyst for propylene polymerization |
| CN100441561C (en) * | 2002-02-07 | 2008-12-10 | 中国石油化工股份有限公司 | Polyester compound for preparing olefine polymerizing catalyst |
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| CN1955195B (en) * | 2005-10-26 | 2010-06-16 | 中国石油化工股份有限公司 | Catalyst, preparation method and application for olefin polymerization or copolymerization |
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| CN102286118B (en) * | 2010-06-18 | 2013-02-27 | 中国石油化工股份有限公司 | Titanium-containing solid catalyst component and catalyst for polymerization of olefin |
| CN102464733A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method thereof as well as olefin polymerization method |
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| CN102838696A (en) * | 2011-06-24 | 2012-12-26 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, olefin polymerization method and applications |
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| CN114456289A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization, and preparation method and application thereof |
| CN114456288A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization reaction, and preparation method and application thereof |
| CN114456288B (en) * | 2020-10-22 | 2024-02-13 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization reaction, preparation method and application thereof |
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