CN103665200A - Solid catalyst component used for olefin polymerization, catalyst and application - Google Patents
Solid catalyst component used for olefin polymerization, catalyst and application Download PDFInfo
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- CN103665200A CN103665200A CN201210328700.4A CN201210328700A CN103665200A CN 103665200 A CN103665200 A CN 103665200A CN 201210328700 A CN201210328700 A CN 201210328700A CN 103665200 A CN103665200 A CN 103665200A
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Abstract
The invention discloses a solid catalyst component used for olefin polymerization. The solid catalyst component contains magnesium, titanium, halogen and an electro donor compound, wherein the electron donor compound is selected from a compound as shown in the following formula (I) which is shown in the specification, wherein R1, R2 and R3 can be the same or different, are selected from hydrogen, C1-C12 alkyl, alkoxy containing C1-C12 alkyl, alkoxy carbonyl containing C1-C12 alkyl and a halogen atom; R4 is selected from C1-C4 alkyl. According to the invention, a novel compound containing a special functional group aromatic carboxylic ester and a diether group is taken as the electron donor to provide a novel solid catalyst component and a catalyst prepared by using the solid catalyst component and a pre-polymerization catalyst; the solid catalyst component has excellent comprehensive performance, and high activity while being used for olefin polymerization, especially propylene polymerization; the obtained polymer is high in isotacticity and has good application prospect.
Description
Technical field
The present invention relates to a kind of ingredient of solid catalyst for olefinic polymerization, more particularly, the present invention relates to the olefins polymerizing solid catalyst component containing a kind of new ether-ether class electron donor compound.The invention still further relates to the catalyzer and the application of this catalyzer in olefinic polymerization that by above-mentioned ingredient of solid catalyst, are prepared.
Technical background
As everyone knows, using magnesium, titanium, halogen and electron donor as the solid titanium catalyst component of basal component, can be used for CH
2=CHR olefinic polyreaction, particularly in the alpha-olefine polymerizing with 3 carbon or more carbon atoms, can obtain the polymkeric substance of higher yields and higher tacticity, wherein electron donor compound is one of requisite composition in catalyst component, and along with the development of internal electron donor compound has caused polyolefin catalyst constantly to update.At present, multiple electron donor compound is disclosed in a large number, such as polycarboxylic acid, monocarboxylic ester or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and derivative thereof, wherein comparatively conventional is aromatic carboxylates's class of binary, such as n-butyl phthalate or diisobutyl phthalate etc.
Summary of the invention
The invention provides a kind of containing novel ether-ether class to the ingredient of solid catalyst of electron compound and the catalyzer of preparation thereof, its high comprehensive performance; Utilize described ingredient of solid catalyst and catalyzer for olefinic polymerization, especially propylene polymerization, has higher activity, and polymkeric substance taxis is good, has good application prospect.
According to an aspect of the present invention, provide a kind of ingredient of solid catalyst for olefinic polymerization, it comprises magnesium, titanium, halogen and electron donor compound, and this electron donor compound is selected from the compound shown in following logical formula I:
R wherein
1, R
2and R
3can be identical or different, be selected from hydrogen, C
1～C
12alkyl, containing C
1～C
12the alkoxyl group of alkyl, containing C
1～C
12the carbalkoxy of alkyl and halogen atom; R
4be selected from C
1～C
4alkyl.
In an embodiment of above-mentioned ingredient of solid catalyst, in the compound shown in described logical formula I, R
1, R
2and R
3be selected from hydrogen, C
1～C
4alkyl, containing C
1～C
4the alkoxyl group of alkyl, containing C
1～C
4the carbalkoxy of alkyl, F, Cl, Br and I, R
4be selected from methyl and ethyl.
In above-mentioned ingredient of solid catalyst, the specific examples of the compound shown in described logical formula I comprises: benzoyloxy-1,3 Propylene Glycol Dimethyl Ether, 2-(2-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(4-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(2-ethylphenyl) methanoyl-1,3-PD dme, 2-(4-ethylphenyl) methanoyl-1,3-PD dme, 2-(2-propyl group phenyl) methanoyl-1,3-PD dme, 2-(4-propyl group phenyl) methanoyl-1,3-PD dme, 2-(2-butyl phenyl) methanoyl-1,3-PD dme, 2-(4-butyl phenyl) methanoyl-1,3-PD dme, 2-(2-isopropyl phenyl) methanoyl-1,3-PD dme, 2-(4-isopropyl phenyl) methanoyl-1,3-PD dme, 2-(2-isobutyl phenenyl) methanoyl-1,3-PD dme, 2-(4-isobutyl phenenyl) methanoyl-1,3-PD dme, 2-(2-tert-butyl-phenyl) methanoyl-1,3-PD dme, 2-(4-tert-butyl-phenyl) methanoyl-1,3-PD dme, 2-(2-chloro-phenyl-) methanoyl-1,3-PD dme, 2-(4-chloro-phenyl-) methanoyl-1,3-PD dme, 2-(2-p-methoxy-phenyl) methanoyl-1,3-PD dme, 2-(4-p-methoxy-phenyl) methanoyl-1,3-PD dme, 2-(2-ethoxyl phenenyl) methanoyl-1,3-PD dme, 2-(4-ethoxyl phenenyl) methanoyl-1,3-PD dme, 2-(2-methoxycarbonyl phenyl) methanoyl-1,3-PD dme, 2-(4-methoxycarbonyl phenyl) methanoyl-1,3-PD dme, 2-(2-butoxy carbonyl phenyl) methanoyl-1,3-PD dme, 2-(4-butoxy carbonyl phenyl) methanoyl-1,3-PD dme, 2-(2-methyl-4-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(2-methyl-4-p-methoxy-phenyl) methanoyl-1,3-PD dme, 2-(2-methoxyl group-4-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(2-ethyl-4-p-methoxy-phenyl) methanoyl-1,3-PD dme, 2-(2-methoxyl group-4-ethylphenyl) methanoyl-1,3-PD dme, 2-(2-methyl-4-methoxycarbonyl phenyl) methanoyl-1,3-PD dme, 2-(2-methoxycarbonyl-4-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(2-ethyl-4-methoxycarbonyl phenyl) methanoyl-1,3-PD dme, 2-(2-methoxycarbonyl-4-ethylphenyl) methanoyl-1,3-PD dme, 2-(2-methyl-4-carbethoxy phenyl) methanoyl-1,3-PD dme, 2-(2-ethoxycarbonyl-4-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(2-methyl-4-butoxy carbonyl phenyl) methanoyl-1,3-PD dme, 2-(2-butoxy carbonyl-4-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(2-ethyl-4-carbethoxy phenyl) methanoyl-1,3-PD dme, 2-(2-ethoxycarbonyl-4-ethylphenyl) methanoyl-1,3-PD dme, 2-(2-ethyl-4-butoxy carbonyl phenyl) methanoyl-1,3-PD dme, 2-(2-butoxy carbonyl-4-ethylphenyl) methanoyl-1,3-PD dme, 2-(2,4,6-trimethylphenyl) methanoyl-1,3-PD dme, 2-(2-aminomethyl phenyl) methanoyl-1,3-PD diethyl ether, the different ether of 2-(4-aminomethyl phenyl) methanoyl-1,3-PD two, 2-(2-ethylphenyl) methanoyl-1,3-PD diethyl ether, 2-(4-ethylphenyl) methanoyl-1,3-PD diethyl ether, 2-(2-propyl group phenyl) methanoyl-1,3-PD diethyl ether, 2-(4-propyl group phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-butyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(4-butyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-isopropyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(4-isopropyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-isobutyl phenenyl) methanoyl-1,3-PD diethyl ether, 2-(4-isobutyl phenenyl) methanoyl-1,3-PD diethyl ether, 2-(2-tert-butyl-phenyl) methanoyl-1,3-PD diethyl ether, 2-(4-tert-butyl-phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-chloro-phenyl-) methanoyl-1,3-PD diethyl ether, 2-(4-chloro-phenyl-) methanoyl-1,3-PD two methyl ethyl ethers, 2-(2-p-methoxy-phenyl) methanoyl-1,3-PD diethyl ether, 2-(4-p-methoxy-phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethoxyl phenenyl) methanoyl-1,3-PD diethyl ether, 2-(4-ethoxyl phenenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methoxycarbonyl phenyl) methanoyl-1,3-PD two methyl ethyl ethers, 2-(4-methoxycarbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-butoxy carbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(4-butoxy carbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methyl-4-aminomethyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methyl-4-p-methoxy-phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methoxyl group-4-aminomethyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethyl-4-p-methoxy-phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methoxyl group-4-ethylphenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methyl-4-methoxycarbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methoxycarbonyl-4-aminomethyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethyl-4-methoxycarbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methoxycarbonyl-4-ethylphenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methyl-4-carbethoxy phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethoxycarbonyl-4-aminomethyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methyl-4-butoxy carbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-butoxy carbonyl-4-aminomethyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethyl-4-carbethoxy phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethoxycarbonyl-4-ethylphenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethyl-4-butoxy carbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-butoxy carbonyl-4-ethylphenyl) methanoyl-1,3-PD diethyl ether or 2-(2,4,6-trimethylphenyl) methanoyl-1,3-PD diethyl ether etc.
Above-mentioned ingredient of solid catalyst, is characterized in that, the gross weight based on ingredient of solid catalyst, and the content of the compound of described logical formula I is 3 ~ 25wt%, and the content of titanium is 1 ~ 8wt%, and the content of magnesium is 8 ~ 30wt%.Preferably, the content of the compound shown in described logical formula I is 5 ~ 25wt%, and the content of titanium is 1 ~ 6wt%, and the content of magnesium is 10 ~ 25wt%.
Ingredient of solid catalyst for olefinic polymerization of the present invention, preferably comprises titanium compound, magnesium compound and is selected from the reaction product with the compound shown in above-mentioned logical formula I.
Wherein magnesium compound used is selected from the derivative that one of them halogen atom in the hydrate of magnesium dihalide, alkoxyl group magnesium ﹑ alkane base magnesium ﹑ magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula is replaced by-oxyl or halo-oxyl; Be preferably the alcohol adduct of magnesium dihalide or magnesium dihalide.Specific examples is as magnesium dichloride, dibrominated magnesium, two magnesium iodides and their alcohol adduct.
Wherein can to select general formula be TiX to titanium compound used
m(OR
1)
4-mcompound, R in formula
1for C
1~ C
20alkyl, X is halogen, 1≤m≤4.For example: titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, preferably titanium tetrachloride.
Compound shown in wherein said logical formula I:
R wherein
1, R
2and R
3can be identical or different, be selected from hydrogen, C
1～C
12alkyl, containing C
1～C
12the alkoxyl group of alkyl, containing C
1～C
12the carbalkoxy of alkyl and halogen atom; R
4be selected from C
1～C
4alkyl.In one embodiment, in the compound shown in described logical formula I, R
1, R
2and R
3be selected from hydrogen, C
1～C
4alkyl, containing C
1～C
4the alkoxyl group of alkyl, containing C
1～C
4the carbalkoxy of alkyl, F, Cl, Br and I, R
4be selected from methyl and ethyl.
Particularly, the specific examples of the compound shown in described logical formula I comprises: benzoyloxy-1,3 Propylene Glycol Dimethyl Ether, 2-(2-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(4-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(2-ethylphenyl) methanoyl-1,3-PD dme, 2-(4-ethylphenyl) methanoyl-1,3-PD dme, 2-(2-propyl group phenyl) methanoyl-1,3-PD dme, 2-(4-propyl group phenyl) methanoyl-1,3-PD dme, 2-(2-butyl phenyl) methanoyl-1,3-PD dme, 2-(4-butyl phenyl) methanoyl-1,3-PD dme, 2-(2-isopropyl phenyl) methanoyl-1,3-PD dme, 2-(4-isopropyl phenyl) methanoyl-1,3-PD dme, 2-(2-isobutyl phenenyl) methanoyl-1,3-PD dme, 2-(4-isobutyl phenenyl) methanoyl-1,3-PD dme, 2-(2-tert-butyl-phenyl) methanoyl-1,3-PD dme, 2-(4-tert-butyl-phenyl) methanoyl-1,3-PD dme, 2-(2-chloro-phenyl-) methanoyl-1,3-PD dme, 2-(4-chloro-phenyl-) methanoyl-1,3-PD dme, 2-(2-p-methoxy-phenyl) methanoyl-1,3-PD dme, 2-(4-p-methoxy-phenyl) methanoyl-1,3-PD dme, 2-(2-ethoxyl phenenyl) methanoyl-1,3-PD dme, 2-(4-ethoxyl phenenyl) methanoyl-1,3-PD dme, 2-(2-methoxycarbonyl phenyl) methanoyl-1,3-PD dme, 2-(4-methoxycarbonyl phenyl) methanoyl-1,3-PD dme, 2-(2-butoxy carbonyl phenyl) methanoyl-1,3-PD dme, 2-(4-butoxy carbonyl phenyl) methanoyl-1,3-PD dme, 2-(2-methyl-4-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(2-methyl-4-p-methoxy-phenyl) methanoyl-1,3-PD dme, 2-(2-methoxyl group-4-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(2-ethyl-4-p-methoxy-phenyl) methanoyl-1,3-PD dme, 2-(2-methoxyl group-4-ethylphenyl) methanoyl-1,3-PD dme, 2-(2-methyl-4-methoxycarbonyl phenyl) methanoyl-1,3-PD dme, 2-(2-methoxycarbonyl-4-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(2-ethyl-4-methoxycarbonyl phenyl) methanoyl-1,3-PD dme, 2-(2-methoxycarbonyl-4-ethylphenyl) methanoyl-1,3-PD dme, 2-(2-methyl-4-carbethoxy phenyl) methanoyl-1,3-PD dme, 2-(2-ethoxycarbonyl-4-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(2-methyl-4-butoxy carbonyl phenyl) methanoyl-1,3-PD dme, 2-(2-butoxy carbonyl-4-aminomethyl phenyl) methanoyl-1,3-PD dme, 2-(2-ethyl-4-carbethoxy phenyl) methanoyl-1,3-PD dme, 2-(2-ethoxycarbonyl-4-ethylphenyl) methanoyl-1,3-PD dme, 2-(2-ethyl-4-butoxy carbonyl phenyl) methanoyl-1,3-PD dme, 2-(2-butoxy carbonyl-4-ethylphenyl) methanoyl-1,3-PD dme, 2-(2,4,6-trimethylphenyl) methanoyl-1,3-PD dme, 2-(2-aminomethyl phenyl) methanoyl-1,3-PD diethyl ether, the different ether of 2-(4-aminomethyl phenyl) methanoyl-1,3-PD two, 2-(2-ethylphenyl) methanoyl-1,3-PD diethyl ether, 2-(4-ethylphenyl) methanoyl-1,3-PD diethyl ether, 2-(2-propyl group phenyl) methanoyl-1,3-PD diethyl ether, 2-(4-propyl group phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-butyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(4-butyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-isopropyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(4-isopropyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-isobutyl phenenyl) methanoyl-1,3-PD diethyl ether, 2-(4-isobutyl phenenyl) methanoyl-1,3-PD diethyl ether, 2-(2-tert-butyl-phenyl) methanoyl-1,3-PD diethyl ether, 2-(4-tert-butyl-phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-chloro-phenyl-) methanoyl-1,3-PD diethyl ether, 2-(4-chloro-phenyl-) methanoyl-1,3-PD two methyl ethyl ethers, 2-(2-p-methoxy-phenyl) methanoyl-1,3-PD diethyl ether, 2-(4-p-methoxy-phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethoxyl phenenyl) methanoyl-1,3-PD diethyl ether, 2-(4-ethoxyl phenenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methoxycarbonyl phenyl) methanoyl-1,3-PD two methyl ethyl ethers, 2-(4-methoxycarbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-butoxy carbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(4-butoxy carbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methyl-4-aminomethyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methyl-4-p-methoxy-phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methoxyl group-4-aminomethyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethyl-4-p-methoxy-phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methoxyl group-4-ethylphenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methyl-4-methoxycarbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methoxycarbonyl-4-aminomethyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethyl-4-methoxycarbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methoxycarbonyl-4-ethylphenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methyl-4-carbethoxy phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethoxycarbonyl-4-aminomethyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-methyl-4-butoxy carbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-butoxy carbonyl-4-aminomethyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethyl-4-carbethoxy phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethoxycarbonyl-4-ethylphenyl) methanoyl-1,3-PD diethyl ether, 2-(2-ethyl-4-butoxy carbonyl phenyl) methanoyl-1,3-PD diethyl ether, 2-(2-butoxy carbonyl-4-ethylphenyl) methanoyl-1,3-PD diethyl ether or 2-(2,4,6-trimethylphenyl) methanoyl-1,3-PD diethyl ether etc.
Ingredient of solid catalyst in the present invention, for example can prepare by the following method: first magnesium compound is dissolved in the solvent system that comprises organic epoxy compounds, organo phosphorous compounds and inert diluent composition, after forming homogeneous solution, mix with titanium compound, under precipitation additive exists, separate out solids; This solids by using is selected from the compound of logical formula I and processes, and it is attached on solids, if desired, then with titanium tetrahalide and inert diluent, solids is processed.
Compound shown in wherein said magnesium compound, titanium compound and logical formula I is as described in aforementioned.Described organic epoxy compounds, organo phosphorous compounds and precipitation additive etc. are disclosed in Chinese patent CN85100997, and its associated viscera is incorporated herein by reference.As organic epoxy compounds can be selected from carbonatoms at oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine.Particular compound is as oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF).As organo phosphorous compounds can comprise hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, concrete as: 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, tricresyl phosphite benzene methyl.As described in precipitation additive optional from organic acid anhydride, organic acid, ether, ketone and ester.Specifically comprise 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, succinate, malonic ester, glutarate, 2,4-pentadiol ester, 3,5-heptanediol ester.Described each component is in every mole of magnesium compound, the consumption of organic epoxy compounds is 0.2～10 mole, the consumption of organo phosphorous compounds is 0.1～3 mole, the consumption of precipitation additive is 0～1.0 mole, the consumption of titanium compound is 0.5～150 mole, and the consumption of the compound shown in described logical formula I is 0.01 ~ 1.0 mole.
Described ingredient of solid catalyst in the present invention also can be prepared by additive method, specifically can comprise the following method of enumerating.
Method one: as according to the disclosed method Kaolinite Preparation of Catalyst of patent CN1506384 component.First, magnesium compound is mixed by 2～5 mol ratios and inert solvent with organic alcohol compound, be warming up to 120～150 ℃, by magnesium/acid anhydride mol ratio 5～10 reaction 1～5 hour.Then according to titanium/magnesium mol ratio 20～50, the alcohol adduct that is chilled to room temperature is joined in advance in the compound titanium solution that is chilled to-15～-40 ℃, be warming up to 90～110 ℃, according to magnesium/internal electron donor mol ratio 2～10, add a kind of being selected to lead to the compound shown in formula I 100～130 ℃ of reactions 1～3 hour, filter to isolate solid particulate.According to titanium/magnesium mol ratio 20～50, solid particulate is joined in compound titanium solution again, stir and 100～130 ℃ of reactions 1.5～3 hours, filter to isolate solid particulate.Finally, with the inert solvent washing solid particulate of 50～80 ℃, after being dried, obtain catalyst component.
Method two: by titanium compound of the present invention, concrete as TiCl
4, with general formula be MgCl
2the adducts reaction of pROH and prepare ingredient of solid catalyst.At MgCl
2in pROH, p is 0.1～6 number, preferably 2～3.5, and R is the alkyl with 1～18 carbon atom.Adducts can be made spherical by the following method aptly: under not existing with the miscible unreactive hydrocarbons of adducts, by alcohol (ROH) and MgCl
2mix, make the rapid chilling of this emulsion, thereby adducts is solidified with the form of spheroidal particle.The adducts so obtaining can directly react with titanium compound, or its dealcoholization (80～130 ℃) that can pass through thermal control in advance before reacting with titanium compound is to obtain a kind of adducts, wherein the mole number of alcohol is generally lower than 3, preferably between 0.1 and 2.7.Can be by adducts (dealcoholysis or itself) be suspended in to cold TiCl
4in (general 0 ℃), and by mixture temperature programming to 80～130 ℃ and keep at this temperature 0.1～2 hour, carry out and the reacting of titanium compound.TiCl
4processing can be carried out once or repeatedly.Using TiCl
4during processing, can add the logical formula I compound of above-mentioned the present invention to process, this processing also can repeat once or repeatedly.
Method three: according to the disclosed method Kaolinite Preparation of Catalyst of patent CN1091748 component.Magnesium chloride alcohol adduct melt disperses through high-speed stirring in the dispersant system of white oil and silicone oil, forms emulsion, is discharged into rapid cooling and shaping in cooling fluid, forms magnesium chloride alcohol adduct microballoon.Cooling fluid is the inert hydrocarbon solvent that boiling point is lower, as sherwood oil, pentane, hexane, heptane etc.Gained magnesium chloride alcohol adduct microballoon through washing, be dried as ball type carrier, the mol ratio of its alcohol and magnesium chloride is 2～3, with 2～2.5 for well.Diameter of carrier is 10～300 microns, best with 30～150 microns.
With excessive titanium tetrachloride, at the above-mentioned ball type carrier of subzero treatment, progressively heat up, in treating processes, add the electron donor shown in the logical formula I of the present invention, after processing, with inert solvent, repeatedly wash, after being dried, obtain the spherical catalyst component of solid powdery.The mol ratio of titanium tetrachloride and magnesium chloride is 20～200, with 30～60 for well; Initiated process temperature is-30～0 ℃, take-25～-20 ℃ as good; Final treatment temp is 80～136 ℃, take 100～130 ℃ as good.
Method four: also available dialkoxy magnesium adds in arene compound and stirs, forms suspension; Suspension uses tetravalence titanium chloride-20～100 ℃ of processing, and 0～130 ℃ of reaction, in this process, at-20～130 ℃, adds the logical formula I electron donor of the present invention to react, and the solid obtaining washs with arene compound; Then at 0～130 ℃ in aromatic hydrocarbon solvent, then process with tetravalence titanium chloride, finally, with inert solvent washing, drain, obtain ingredient of solid catalyst.Tetravalence titanium chloride 0.5～100mol for every mole of dialkyl magnesium wherein, 0.01～10mol for electron donor.
Method five: use TiCl
4or its aromatic hydrocarbons solution carries out halogenation to two magnesium alkoxide compounds such as dialkoxy magnesium or two aryloxy magnesium at 80～130 ℃, use TiCl
4or its aromatic hydrocarbons solution processes and can repeat one or many, and in the such processing of one or many, add the compound of the logical formula I of the present invention.
Method six: according to the disclosed method Kaolinite Preparation of Catalyst of patent US4540679 component.First, magnesium alkoxide and carbon dioxide reaction make alkyl magnesiumcarbonate carrier.Then transistion metal compound (being preferably tetravalent titanium compound) and alkyl magnesiumcarbonate carrier react in certain proportion with the electron donor of the logical formula I of the present invention in inert solvent, wherein the mol ratio of transition metal and magnesium elements is at least 0.5:1, and the electron donor consumption of the logical formula I of the present invention mostly is 1.0 moles of every gram of titanium atoms most.Inert solvent must, through purifying, easily make the material of poisoning of catalyst to slough water, oxygen, carbonic acid gas etc.Reaction is carried out at-10～170 ℃, and the reaction times is that several minutes arrives several hours.
The method of preparing ingredient of solid catalyst is also just like by magnesium compound, and electron donor etc. form emulsion in thinner, add titanium compound to make it fixedly obtain spherical solid, the more treated ingredient of solid catalyst that obtains.
In any above-mentioned preparation method, needed electron donor compound (I) can add with the form of compound; Also can add in other mode, as can be by adopting the applicable precursor original position of electron donor compound (I) to obtain, this front physical efficiency by example as is known chemical reaction become needed electron donor compound as esterification etc.
According to another aspect of the present invention, provide a kind of catalyzer for olefinic polymerization, it comprises the product that following component reaction obtains:
A) above-mentioned ingredient of solid catalyst;
B) alkylaluminium cpd, general formula is AlR
nx
3-n, in formula, R is hydrogen, C
1～C
20alkyl, X is halogen, 1 < n≤3.
In above-mentioned catalyzer, the specific examples of described alkylaluminium cpd comprises triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride and ethyl aluminum dichloride, preferably triethyl aluminum, triisobutyl aluminium.
When needing the application of the very high olefin polymer of taxis, need add external electron donor amount of component b in described catalyzer).Described external electron donor amount of component b) being selected from general formula is R
2ksi (OR
3)
4-kcompound, 0≤k≤3 in formula, R
2and R
3identical or different, R
3be selected from alkyl, cycloalkyl, aryl, haloalkyl, R
2be selected from alkyl, cycloalkyl, aryl, haloalkyl, amino, substituted-amino, halogen and hydrogen atom.For example: trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, methyl-t-butyldimethoxysilane, preferably Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane.
In above-mentioned catalyzer, described component a) and components b) mol ratio with titanium: aluminium is counted 1:5 ~ 5000, preferably 1:20 ~ 500.Component a) and amount of component b) mol ratio with titanium: silicon is counted 1:0 ~ 500, preferably 1:3 ~ 100.
According to another aspect of the present invention, a kind of pre-polymerized catalyst for olefinic polymerization is provided, described pre-polymerized catalyst comprises the prepolymer that above-mentioned catalyzer and alkene carry out prepolymerization gained, and pre-polymerization multiple is 0.1 ~ 1000g olefin polymer/g ingredient of solid catalyst.
In the present invention, " pre-polymerized catalyst " refers to the catalyzer through polymerization procedure with lower transforming degree.According to the present invention, can adopt the alpha-olefin identical with polymerization alkene used to carry out prepolymerization, wherein carry out prepolymerized alkene and be preferably ethene or propylene.Specifically, particularly preferably be, the mixture that adopts ethene or itself and amount to be up to one or more alpha-olefins of 20mol% carries out prepolymerization.Preferably, the transforming degree of pre-polymerized catalyst components is approximately 0.2～500 gram of polymkeric substance/gram ingredient of solid catalyst.
Prepolymerization operation can, at-20 to 80 ℃, preferably, at the temperature of 0～50 ℃, be carried out in liquid or in gas phase.The part that prepolymerization step can be used as in continuous polymerization technique is carried out online, or carries out independently in periodical operation.For preparation amount is the polymkeric substance of 0.5～20g/g catalyst component, the batch pre-polymerization of catalyzer of the present invention and ethene particularly preferably.Polymerization pressure is 0.01～10MPa.
According to a further aspect in the invention, provide a kind of olefine polymerizing process, wherein said alkene carries out polymerization under the effect of above-mentioned catalyzer or pre-polymerized catalyst.
Catalyzer of the present invention can directly add in reactor for polymerization process, or catalyzer and alkene pre-polymerization obtain adding in reactor after pre-polymerized catalyst.
Olefinic polyreaction of the present invention carries out according to known polymerization process, can in liquid phase or gas phase, carry out, or also can under the operation of liquid and gas polymerization stage combination, carry out.Adopt conventional technology as slurry process, gas-phase fluidized-bed etc.To adopt following reaction conditions preferably: 0～150 ℃ of polymerization temperature, preferably 60～90 ℃.In a specific embodiment, described in be polymerized to slurry polymerization.
The general formula of alkene described in the present invention is CH
2=CHR, wherein R is hydrogen or C
1～C
12alkyl or aryl.As be selected from ethene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene.Be preferably selected from ethene and propylene.As the equal polymerization of propylene with or the copolymerization of other alkene of propylene.The inventive method is also applicable to as the homopolymerization of ethene and ethene and alpha-olefin, as the copolymerization of propylene, butylene, amylene, hexene, octene, 4-methyl-1-pentene.
The present invention is by adopting a kind of new compound that contains particular functional group's aromatic carboxylic acid esters and two ether group combinations as internal electron donor, the catalyzer and the pre-polymerized catalyst that a kind of new ingredient of solid catalyst are provided and have used described ingredient of solid catalyst to prepare, its high comprehensive performance, for olefinic polymerization, especially during propylene polymerization, have higher activity, resulting polymers degree of isotacticity is high, has good application prospect.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but do not form any limitation of the invention.
Testing method
The mensuration of nucleus magnetic resonance: use Bruke dmx300 nuclear magnetic resonance analyser Instrument measuring
1h-NMR(300MHz, solvent C DCl
3, TMS is interior mark, measures temperature 300K).
Polymkeric substance isotactic index: adopt heptane extraction process to measure (heptane boiling extracting 6 hours): 2 grams of dry polymer samples, be placed in extractor and use the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to constant weight gained is isotactic index with 2 ratio.
One, compound is synthetic
Compound (1)
Synthetic aromatic carboxylic acid esters diether compounds (1) has following structure:
The 1st step: epoxy chloropropane and methyl alcohol, under the effect of NaOH, be take to excessive methyl alcohol as solvent refluxing reaction 6 hours, obtain 1,3-dimethoxy-2-propyl alcohol; In molar ratio, epoxy chloropropane: NaOH is 1: 1.05; The consumption of described methanol solvate is by adding the described methanol solvate of 0.6L in every moles of epichlorohydrin substrate.
The 2nd step: by 1 of gained, 3-dimethoxy-2-propyl alcohol and 4-n-butylbenzene formyl chloride are under the effect of acid binding agent triethylamine, and back flow reaction is 7 hours in tetrahydrofuran solvent, obtains carboxylate aryl's diether compounds (1);
In molar ratio, 1,3-dimethoxy-2-propyl alcohol: 4-n-butylbenzene formyl chloride: triethylamine=1:1:1.5;
The consumption of described tetrahydrofuran (THF), by every mole 1, adds the tetrahydrofuran (THF) of 1.5L in 3-dimethoxy-2-propyl alcohol substrate.
With
1h NMR has confirmed the structure of carboxylate aryl's diether compounds (1) of synthesized.
1h NMR (300MHz, CDCl
3, TMS is interior mark, δ/ppm): 7.96-7.99,7.22-7.25 (m, 4H), 5.34-5.41 (m, 1H), 3.67 (dd, 4H), 3.39 (s, 6H), 2.65 (t, 2H), 1.55-1.65 (m, 2H), 1.28-1.41 (m, 2H), 0.92 (t, 3H).
Compound (2)～(13)
According to the synthetic method similar to above-claimed cpd (1), select different low-carbon alcohol R
4the substituted benzoyl chloride that OH and structural formula are (II) is raw material, synthesizes and obtains a series of aromatic carboxylic acid esters diether compounds (2)～(13) with logical formula I.And use
1h NMR has confirmed the structure of synthesized compound.Low-carbon alcohol R
4r in OH and substituted benzoyl chloride (II) and product structure formula I
1, R
2, R
3and R
4in Table 1.
Table 1 aromatic carboxylic acid esters diether compounds
Two, the preparation of ingredient of solid catalyst and application
Embodiment 1
In the reactor of fully replacing through high pure nitrogen, add successively magnesium chloride 4.8g, toluene 95mL, epoxy chloropropane 4mL, tributyl phosphate 12.5mL, is warming up to 50 ℃, and maintains 2.5h under stirring, solid dissolves completely, adds Tetra hydro Phthalic anhydride 1.4g, continues to maintain 1h.Solution is cooled to below-25 ℃, in 1h, drips TiCl
456mL, slowly be warming up to 80 ℃, in temperature-rise period, separate out gradually solids, the compound (1) that adds the above-mentioned preparation of 6mmol: 2-(4-n-butylphenyl) methanoyl-1, ammediol dme is as internal electron donor, and holding temperature 1h, after filtration, use respectively toluene 70mL washed twice, obtain solid sediment.Then add toluene 60mL, TiCl
440mL, is warmed up to 110 ℃, maintains 2h, and after venting filtrate, same operation repeats once, then at 110 ℃, washs three times with toluene 70mL, and the time is respectively 10min, then adds hexane 60mL, washed twice.Obtain ingredient of solid catalyst.
After dry 250mL there-necked flask is fully replaced with nitrogen and propylene respectively, add 100mL heptane, be heated to after 70 ℃, under normal pressure, add a certain amount of AlEt
3and Cyclohexylmethyldimethoxysilane (CHMMS), guarantee Al/Si=20 (mol), at this temperature, add the catalyst component of above-mentioned preparation, reaction 2h, uses ethanol termination reaction.Polymkeric substance absolute ethanol washing, vacuum-drying obtains polymkeric substance.Testing data is in Table 2.
Embodiment 2
Method is with embodiment 1, and difference is that added internal electron donor is compound (2): 2-(2-ethoxyl phenenyl) methanoyl-1,3-PD dme.Data are in Table 2.
Embodiment 3
Method is with embodiment 1, and difference is that added internal electron donor is compound (3): 2-(2,4,6-trimethylphenyl) methanoyl-1,3-PD dme.Data are in Table 2.
Embodiment 4
Method is with embodiment 1, and difference is that added internal electron donor is compound (4): 2-(4-tert-butyl-phenyl) methanoyl-1,3-PD dme.Data are in Table 2.
Embodiment 5
Method is with embodiment 1, and difference is that added internal electron donor is compound (5): 2-(2-aminomethyl phenyl) methanoyl-1,3-PD dme.Data are in Table 2.
Embodiment 6
Method is with embodiment 1, and difference is that added internal electron donor is compound (6): 2-benzoyloxy-1,3-PD dme.Data are in Table 2.
Embodiment 7
Method is with embodiment 1, and difference is that added internal electron donor is compound (7): 2-(2-chloro-phenyl-) methanoyl-1,3-PD dme.Data are in Table 2.
Embodiment 8
Method is with embodiment 1, and difference is that added internal electron donor is compound (8): 2-(2-p-methoxy-phenyl) methanoyl-1,3-PD dme.Data are in Table 2.
Embodiment 9
Method is with embodiment 1, and difference is that added internal electron donor is compound (9): 2-(4-aminomethyl phenyl) methanoyl-1,3-PD dme.Data are in Table 2.
Embodiment 10
Method is with embodiment 1, and difference is that added internal electron donor is compound (10): 2-(2-methoxycarbonyl phenyl) methanoyl-1,3-PD dme.Data are in Table 2.
Embodiment 11
Method is with embodiment 1, and difference is that added internal electron donor is compound (11): 2-(2-butoxy carbonyl phenyl) methanoyl-1,3-PD dme.Data are in Table 2.
Embodiment 12
Method is with embodiment 1, and difference is that added internal electron donor is compound (12): 2-(2-methoxycarbonyl phenyl) methanoyl-1,3-PD diethyl ether.Data are in Table 2.
Embodiment 13
Method is with embodiment 1, and difference is that added internal electron donor is compound (13): 2-(2-butoxy carbonyl phenyl) methanoyl-1,3-PD diethyl ether.Data are in Table 2.
Table 2 catalyst propylene polymerization result
As can be seen from Table 2, adopt a kind of new compound that contains particular functional group's aromatic carboxylic acid esters and two ether group combinations as electron donor, the ingredient of solid catalyst of preparation and catalyzer, for olefinic polymerization, have good activity and higher degree of isotacticity.
It should be noted in the discussion above that above-described embodiment, only for explaining the present invention, does not form any limitation of the invention.By with reference to exemplary embodiments, invention has been described, but should be understood to word wherein used, be descriptive and explanatory vocabulary, rather than limited vocabulary.Can in the scope of the claims in the present invention, to the present invention, modify in accordance with regulations, and within not deviating from scope and spirit of the present invention, the present invention be revised.Although the present invention who wherein describes relates to specific method, material and embodiment, and does not mean that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention can extend to other all methods and applications with identical function.
Claims (13)
1. for an ingredient of solid catalyst for olefinic polymerization, it comprises magnesium, titanium, halogen and electron donor compound, and this electron donor compound is selected from the compound shown in following logical formula I:
R wherein
1, R
2and R
3can be identical or different, be selected from hydrogen, C
1～C
12alkyl, containing C
1～C
12the alkoxyl group of alkyl, containing C
1～C
12the carbalkoxy of alkyl and halogen atom; R
4be selected from C
1～C
4alkyl.
2. ingredient of solid catalyst according to claim 1, is characterized in that, in the compound shown in described logical formula I, and R
1, R
2and R
3be selected from hydrogen, C
1～C
4alkyl, containing C
1～C
4the alkoxyl group of alkyl, containing C
1～C
4the carbalkoxy of alkyl, F, Cl, Br and I, R
4be selected from methyl and ethyl.
3. ingredient of solid catalyst according to claim 1 and 2, is characterized in that, the gross weight based on ingredient of solid catalyst, and the content of the compound shown in described logical formula I is 3 ~ 25wt%, and the content of titanium is 1 ~ 8wt%, and the content of magnesium is 8 ~ 30wt%.
4. ingredient of solid catalyst according to claim 3, is characterized in that, the gross weight based on ingredient of solid catalyst, and the content of the compound shown in described logical formula I is 5 ~ 25wt%, and the content of titanium is 1 ~ 6wt%, and the content of magnesium is 10 ~ 25wt%.
5. according to the catalyst component for olefinic polymerization described in claim 1～4 any one, it comprises titanium compound, magnesium compound and is selected from the reaction product of the compound shown in logical formula I;
Wherein said magnesium compound is selected from the derivative that one of them halogen atom in the hydrate of magnesium dihalide, alkoxyl group magnesium ﹑ alkane base magnesium ﹑ magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula is replaced by-oxyl or halo-oxyl;
Titanium compound is that general formula is TiX
m(OR
1)
4-m, compound, R in formula
1for C
1~ C
20alkyl, X is halogen, 1≤m≤4.
6. for the catalyzer of olefinic polymerization, the reaction product that it comprises following component:
A) ingredient of solid catalyst described in any one in claim 1～5;
B) alkylaluminium cpd, general formula is AlR
nx
3-n, in formula, R is hydrogen, C
1～C
20alkyl, X is halogen, 1 < n≤3.
7. catalyzer according to claim 6, is characterized in that, adds external electron donor amount of component b in described catalyzer), it is selected from general formula is R
2ksi (OR
3)
4-kcompound, 0≤k≤3 in formula, R
3be selected from alkyl, cycloalkyl, aryl, haloalkyl, R
2be selected from alkyl, cycloalkyl, aryl, haloalkyl, amino, substituted-amino, halogen and hydrogen atom.
8. according to the catalyzer described in claim 6 or 7, it is characterized in that, described component a) and b) mol ratio with titanium: aluminium is counted 1:5 ~ 5000, preferably 1:20 ~ 500.
9. catalyzer according to claim 7, is characterized in that, described component a) and c) mol ratio with titanium: silicon is counted 1:0 ~ 500, preferably 1:3 ~ 100.
10. the pre-polymerized catalyst for olefinic polymerization, described pre-polymerized catalyst comprises a kind of prepolymer that carries out prepolymerization gained according to the catalyzer described in any one in claim 6 ~ 9 and alkene, and pre-polymerization multiple is 0.1 ~ 1000g olefin polymer/g ingredient of solid catalyst.
11. pre-polymerized catalysts according to claim 10, is characterized in that, prepolymerization alkene used is ethene or propylene.
The method of 12. 1 kinds of olefinic polymerizations, wherein said alkene carries out polymerization under the effect of the pre-polymerized catalyst described in any one in the catalyzer described in any one or claim 10 ~ 11 in claim 6 ~ 9.
13. methods according to claim 12, is characterized in that, the general formula of described alkene is CH
2=CHR, wherein R is hydrogen or C
1~ C
12alkyl or aryl, be preferably selected from ethene or propylene.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5730708A (en) * | 1980-07-30 | 1982-02-19 | Mitsui Toatsu Chem Inc | Stereoregular polymerizing method of alpha-olefin |
| CN1690039A (en) * | 2004-04-30 | 2005-11-02 | 中国石油化工股份有限公司 | Diester compound for preparing olefinic polymerization catalyst |
| CN101759564A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Ester compound and application thereof in catalyst for olefin polymerization |
| CN102040679A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefinic polymerization reaction |
-
2012
- 2012-09-06 CN CN201210328700.4A patent/CN103665200B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5730708A (en) * | 1980-07-30 | 1982-02-19 | Mitsui Toatsu Chem Inc | Stereoregular polymerizing method of alpha-olefin |
| CN1690039A (en) * | 2004-04-30 | 2005-11-02 | 中国石油化工股份有限公司 | Diester compound for preparing olefinic polymerization catalyst |
| CN101759564A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Ester compound and application thereof in catalyst for olefin polymerization |
| CN102040679A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefinic polymerization reaction |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160039954A1 (en) * | 2014-08-05 | 2016-02-11 | Basf Corporation | Solid catalyst components for olefin polymerization and methods of making and using the same |
| US9663595B2 (en) * | 2014-08-05 | 2017-05-30 | W. R. Grace & Co. —Conn. | Solid catalyst components for olefin polymerization and methods of making and using the same |
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