CN103626893B - For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction - Google Patents
For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction Download PDFInfo
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Abstract
The invention provides a kind of catalyst component for olefinic polyreaction and catalyzer thereof, described catalyst component comprises the reaction product of magnesium compound, titanium compound and a, b two kind of two ethers electron donor compound, when described catalyzer is used for propylene polymerization, gratifying polymerization yield rate can be obtained, and polymkeric substance degree of isotacticity is high, molecular weight distribution is wider, hydrogen response is better, even if under the polymerizing condition of higher hydrogen gas concentration, resulting polymers degree of isotacticity still can remain on higher level, meets the demand of suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of ingredient of solid catalyst for olefinic polymerization and catalyzer thereof, more particularly, relate to a kind of by two kinds of composite catalyst component and application thereof doing internal electron donor of electron donor.
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 olefinic polyreaction, particularly at the alpha-olefine polymerizing with 3 carbon or more carbon atom, wherein electron donor compound is one of requisite composition in catalyst component, and constantly updates along with the development of internal electron donor compound result in polyolefin catalyst.At present, aromatic carboxylates's class of binary that comparatively conventional is, such as n-butyl phthalate or diisobutyl phthalate etc., as Chinese patent CN85100997A.
In recent years, people attempt again the compound adopting other, as diether, as in olefin polymerization catalyst components electron donor use, such as, disclosed in Chinese patent CN96107325.X and CN89107675.1 in the catalyst component of olefinic polyreaction, have employed 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2, the diether compounds such as 2-diisobutyl-1,3-Propanal dimethyl acetal and 9,9-bis-(methoxymethyl) fluorenes are as electron donor.But the above-mentioned disclosed catalyzer ubiquity molecular weight distribution in the practical application of olefinic polymerization prepared using diether compound as internal electron donor is narrow, unmanageable defect, disclosed in Chinese patent CN102040485 and CN102040684 in the catalyst component of olefinic polyreaction, have employed 2-n-pentyl-2-(2-ethylhexyl)-1, 3-Propanal dimethyl acetal, 2-isopentyl-2-benzyl-1, 3-Propanal dimethyl acetal etc. 1, 3-diether compound is as electron donor, although can the molecular weight distribution of broadening polymkeric substance in the practical application of olefinic polymerization with this type of catalyzer, but in the course of the polymerization process, the concentration of hydrogen when improving polymerization, the degree of isotacticity of polymkeric substance can be caused sharply to decline, the concentration of hydrogen not only cannot be utilized preferably to regulate the molecular weight of final polymkeric substance, also easily cause the blocking of conversion unit, be difficult to realize suitability for industrialized production.
The present inventor have been surprisingly found that, when preparing olefin polymerization catalysis, adopt the diether compound of two kinds of different structures as internal electron donor, by the synergy of these two kinds of diether compounds, prepared catalyzer, not only remain the advantage of the high hydrogen response of catalyzer, and the molecular weight distribution of resulting polymers is wider, even if the more important thing is under the polymerizing condition of high hydrogen concentration, resulting polymers still has higher degree of isotacticity, solves the technical barrier that above-mentioned two ethers catalyzer are run in process of production.
Summary of the invention
One of the object of the invention there is provided a kind of catalyst component for olefinic polymerization, comprises the reaction product of magnesium compound, titanium compound and a, b two kind of two ethers electron donor compound,
Electron donor a is selected from the one in the diether compound of following logical formula I:
In formula: R is C
1~ C
10alkyl, preferably methyl, ethyl;
R
1a kind of C
2~ C
7the alkyl of straight or branched, or the H in described alkyl is optionally by a hybrid atom MCM-41, and described heteroatoms is selected from F, Cl, Br or I, preferably C
2~ C
7the alkyl of straight or branched;
R
2with R
1difference is C
6~ C
10aryl, aralkyl or alkaryl or (R
3r
4)-CH-CH
2-group, wherein R
3, R
4group is identical or different, is selected from C respectively
1~ C
10straight chained alkyl, but R
3with R
4asynchronously CH
3, or R
3with R
4the H be connected with each other in formation cycloalkyl or above-mentioned group is optionally by a hybrid atom MCM-41, and described heteroatoms is selected from F, Cl, Br or I; Be preferably phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, Cvclopropvlmethvl or cyclobutylmethyl.
The example of electron donor a appropriate compound includes but not limited to:
2-ethyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-phenyl-1,3-Propanal dimethyl acetal, 2-normal-butyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-n-pentyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-phenyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-ethyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-benzyl-1,3-Propanal dimethyl acetal, 2-normal-butyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-n-pentyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-benzyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-ethyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-propyl group-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-normal-butyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-n-pentyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-ethyl-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-propyl group-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-normal-butyl-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-n-pentyl-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-ethyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-propyl group-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-normal-butyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-ethyl-2-Cvclopropvlmethvl-1,3-Propanal dimethyl acetal, 2-propyl group-2-Cvclopropvlmethvl-1,3-Propanal dimethyl acetal, 2-normal-butyl-2-Cvclopropvlmethvl-1,3-Propanal dimethyl acetal, 2-n-pentyl-2-Cvclopropvlmethvl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-Cvclopropvlmethvl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-Cvclopropvlmethvl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-Cvclopropvlmethvl-1,3-Propanal dimethyl acetal, 2-ethyl-2-cyclobutylmethyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-cyclobutylmethyl-1,3-Propanal dimethyl acetal, 2-normal-butyl-2-cyclobutylmethyl-1,3-Propanal dimethyl acetal, 2-n-pentyl-2-cyclobutylmethyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclobutylmethyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-cyclobutylmethyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-cyclobutylmethyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-phenyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-(2-methyl butyl)-2-benzyl-1,3-Propanal dimethyl acetal, 2-(2-ethyl-butyl)-2-phenyl-1,3-Propanal dimethyl acetal, 2-(2-ethylhexyl)-2-phenyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-benzyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-(2-methyl butyl)-2-benzyl-1,3-Propanal dimethyl acetal, 2-(2-ethyl-butyl)-2-benzyl-1,3-Propanal dimethyl acetal, 2-(2-ethylhexyl)-2-benzyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-(2-methyl butyl)-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-(2-ethylhexyl)-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-(2-ethyl-butyl)-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-(2-ethylhexyl)-2-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-Cvclopropvlmethvl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-Cvclopropvlmethvl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-cyclobutylmethyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-cyclobutylmethyl-1,3-Propanal dimethyl acetal.
Electron donor b is selected from the one in the diether compound of following logical formula II:
In logical formula II, R ' is identical or not identical, is selected from the C of hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20cyclophane base, C
7-C
20one in aralkyl; Be preferably hydrogen, halogen atom or C
1~ C
6alkyl;
R
1identical or not identical, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20cyclophane base, C
7-C
20one in aralkyl, is preferably hydrogen, methyl or ethyl;
R
2identical or not identical, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20cyclophane base, C
7-C
20one in aralkyl, is preferably methyl or ethyl.
The example of electron donor b appropriate compound includes but not limited to:
Two (methoxymethyl) indenes of 1,1-, 1,1-two (methoxymethyl)-2,3-dimethoxy indenes, 1,1-two (methoxymethyl)-4,5,6,7-tetrafluoro indenes, 1,1-two (methoxymethyl)-2,3,6,7-tetrafluoro indenes, 1,1-two (methoxymethyl)-4,7 dimethyl indenes, 1,1-two (methoxymethyl)-3,6 dimethyl indenes, two (the methoxymethyl)-4-phenylindan of 1-, two (the methoxymethyl)-4-phenyl-2-methyl indenes of 1,1-, two (the methoxymethyl)-4-cyclohexyl indenes of 1,1-, two (methoxymethyl)-7-(3,3, the 3 trifluoro propyls) indenes of 1,1-, two (the methoxymethyl)-7-trimethyl silyl indenes of 1,1-, two (the methoxymethyl)-7-trifluoromethyl indenes of 1,1-, 1,1-two (methoxymethyl)-4,7 dimethyl 4,5,6,7-tetrahydroindene, 1,1-two (methoxymethyl)-7 methyl indenes, two (the methoxymethyl)-7-cyclopentyl indenes of 1,1-, two (the methoxymethyl)-7-sec.-propyl indenes of 1,1-, two (the methoxymethyl)-7-cyclohexyl indenes of 1,1-, 1,1-two (methoxymethyl)-7 tertiary butyl indenes, 1,1-two (methoxymethyl)-7 tertiary butyl 2 methyl indenes, two (the methoxymethyl)-7-phenylindan of 1,1-, two (the methoxymethyl)-2-phenylindan of 1,1-, two (methoxymethyl) fluorenes of 9,9-, 9,9-two (methoxymethyl)-2,3,6,7-tetramethyl-fluorenes, 9,9-two (methoxymethyl)-2,3,4,5,6,7-hexafluoro fluorenes, 9,9-two (methoxymethyl)-2,3-phenylpropyl alcohol indenes, 9,9-two (methoxymethyl)-2,3,6,7-bis-phenylpropyl alcohol indenes, 9,9-two (methoxymethyl)-2,7-bicyclopentyl fluorenes, 9,9-two (methoxymethyl)-1,8-dichloro fluorenes, 9,9-two (methoxymethyl)-2,7-bicyclopentyl fluorenes, 9,9-two (methoxymethyl)-1,8-difluoro fluorenes, 9,9-two (methoxymethyl)-1,2,3,4-tetrahydrochysene fluorenes, 9,9-two (methoxymethyl)-1,2,3,4,5,6,7,8-octahydro fluorenes, two (the methoxymethyl)-4-tert-butyl fluorenes of 9,9-, two (α-methoxy base pitch base) indenes of 1,1-, two (phenoxymethyl) indenes of 1,1-, 1,1-two (1'-methoxy ethyl)-5,6-dichloro indenes, 1,1-two (phenoxymethyl)-3,6-bis-ring ethyl indenes, 1-methoxymethyl-1-(1'-methoxy ethyl)-7 tertiary butyl indenes, two [2-(2' methoxy-propyl)]-2 methyl indenes of 1,1-, 9,9 pairs of (α-p-methoxy-phenyl) fluorenes, two (1'-isopropoxy-normal-butyl)-4, the 5-diphenylfluorene of 9,9-, two (1'-methoxy ethyl) fluorenes of 9,9-, 9-(methoxymethyl)-9-(1' methoxy ethyl)-2,3,6,7-tetrafluoro fluorenes, 9-(methoxymethyl)-9 pentyloxy methyl fluorenes, 9-(methoxymethyl)-9-ethoxyl methyl fluorenes, 9-(methoxymethyl)-9-(1'-methoxy ethyl) fluorenes, 9-(methoxymethyl)-9-[2-(2' methoxy-propyl)] fluorenes, two (methoxymethyl) benzo naphthalene of 1,1-, two (methoxymethyl)-Isosorbide-5-Nitrae-methane dihydronaphthalene of 9,9-, 9,9-is two-(methoxymethyl)-9,10-dihydroanthracene, 1,1-is two-(methoxymethyl)-1,2-dihydroanthracene, two (the methoxymethyl)-1-phenyl-Isosorbide-5-Nitrae-dihydronaphthalene of 4,4-, two (methoxymethyl)-1-phenyl-3, the 4-dihydronaphthalene of 4,4-.
In every mole of magnesium, electron donor compound a add-on is 0.01 ~ 0.5 mole, and the mol ratio of a and b is 0.05 ~ 10; Preferred electron donor compound a add-on is 0.02 ~ 0.2 mole, and the mol ratio of a and b is 0.1 ~ 1.In order to ensure that final resulting polymers has higher degree of isotacticity, in the preferred self-drifting of electron donor compound a (I), R is methyl or ethyl, R
1c
2~ C
7the alkyl of straight or branched and R
2be the compound of phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, Cvclopropvlmethvl or cyclobutylmethyl, the R ' in the preferred self-drifting of electron donor compound b (II) is hydrogen, halogen atom or C
1~ C
6alkyl, R
1hydrogen, methyl or ethyl, R
2it is the compound of methyl or ethyl.
Magnesium compound used be selected from one of them halogen atom in magnesium dihalide, the hydrate of magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula by-oxyl or halo-oxyl the one in the derivative of replacing, or their mixture, preferred magnesium dihalide, such as magnesium dichloride, dibrominated magnesium, diiodinating magnesium.
Titanium compound used can select general formula to be TiX
i n(OR
i)
4-ncompound, R in formula
ifor carbonatoms is the alkyl of 1 ~ 20, X
ifor halogen, n=1 ~ 4.Such as: titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium, preferred titanium tetrachloride.
In catalyst component, the mol ratio of titanium atom and magnesium atom is 0.01 ~ 0.5, is preferably 0.02 ~ 0.1.
Another object of the present invention is to provide a kind of catalyzer for olefinic polyreaction, comprises the reaction product of following component:
(1) above-mentioned catalyst component
(2) alkylaluminium cpd;
(3) optionally, external electron donor component.
Wherein alkylaluminium cpd is general formula is AlR
iI nx
iI 3-ncompound, R in formula
iIfor hydrogen, carbonatoms is the alkyl of 1 ~ 20, X
iIfor halogen, n is the number of 1<n≤3; Specifically can be selected from 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 ethylmercury chloride aluminium, ethyl aluminum dichloride, preferred triethyl aluminum, triisobutyl aluminium.
During to the olefin polymer application needing taxis very high, need add (3) external donor compound, such as general formula is R
iII nsi (OR
iV)
4-nsilicoorganic compound, 0≤n≤3 in formula, R
iIIand R
iVfor of the same race or different alkyl, cycloalkyl, aryl, haloalkyl, R also can be halogen or hydrogen atom.Such as: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, methyl-t-butyldimethoxysilane, preferred Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane.
Wherein component (1), ratio between component (2) and component (3), with titanium: aluminium: the molar ratio computing between silicon is 1:(5 ~ 1000): (0 ~ 500), is preferably 1:(25 ~ 100): (25 ~ 100).
Olefinic polyreaction of the present invention carries out according to known polymerization process, can carry out in liquid phase or gas phase, or also can carry out under the operation of liquid and gas polymerization stage combination, adopt conventional technology, as slurry process, gas-phase fluidized-bed etc., wherein alkene is selected from ethene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene, all polymerizations of special propylene with or the copolymerization of other alkene of propylene, be adopt following reaction conditions preferably:
Polymerization temperature: 0 ~ 150 DEG C, preferably 60 ~ 90 DEG C.
Catalyzer of the present invention can directly add in reactor in polymerization process, or catalyzer can carry out prepolymerization before adding first polymerization reactor, in the present invention, term " pre-polymerized catalyst " means with the catalyzer of lower transforming degree through polymerization procedure.According to the present invention, described pre-polymerized catalyst comprises the prepolymer that above-mentioned ingredient of solid catalyst and alkene carry out prepolymerization gained, and pre-polymerization multiple is 0.1 ~ 1000g olefin polymer/g ingredient of solid catalyst.
The alpha-olefin identical with foregoing alkenes can be adopted to carry out prepolymerization, wherein carry out prepolymerized alkene and be preferably ethene or propylene, specifically, particularly preferably be, the mixture adopting propylene or other amounts to be up to one or more alpha-olefins of 20mol% carries out prepolymerization, preferably, the transforming degree of pre-polymerized catalyst components is about 0.2 gram to about 500 grams polymkeric substance/gram ingredient of solid catalyst.
Prepolymerization operation can at-20 to 80 DEG C, preferably at the temperature of 0 ~ 50 DEG C, carry out in a liquid or in gas phase, prepolymerization step can carry out online as the part in continuous polymerization technique, or carry out independently in periodical operation, for the polymkeric substance that preparation amount is 0.5 ~ 20g/g catalyst component, the particularly preferably batch pre-polymerization of catalyzer of the present invention and propylene, polymerization pressure is 0.01 ~ 10MPa.
Catalyzer of the present invention is also applicable to produce polyethylene and ethene and alpha-olefin, as the multipolymer of propylene, butylene, amylene, hexene, octene, 4-methyl-1-pentene.
It is worthy of note that the present invention passes through in olefin polymerization catalysis by using the diether compound of two kinds of different structures as electron donor simultaneously, the catalyzer of high comprehensive performance can be obtained, catalyzer not only active high, hydrogen response good, the molecular weight distribution of resulting polymers is wide simultaneously, be conducive to the post-production of polymkeric substance and develop new product grade, even if under the polymerizing condition of high hydrogen concentration, resulting polymers degree of isotacticity is still higher, meets demand of industrial production.
Embodiment
Embodiment given below is in order to the present invention is described, instead of limits the invention.
Testing method:
1, polymkeric substance degree of isotacticity adopts heptane extraction process to measure (heptane boiling extracting 6 hours): 2 grams of dry polymer samples, be placed in extractor and after 6 hours with the extracting of boiling heptane, residuum be dried to the polymer weight (g) of constant weight gained and be degree of isotacticity with the ratio of 2.
2, molecular weight distribution: use PL-GPC220 to measure.
3, melting index MFI measures according to ASTMD1238-99.
Catalyst component preparation method:
Diverse ways can be selected to prepare ingredient of solid catalyst of the present invention, just list the method for several Kaolinite Preparation of Catalyst below, instead of the preparation of catalyzer involved in the present invention is defined in this.
Method one: as the method Kaolinite Preparation of Catalyst disclosed according to patent CN1506384.First, Magnesium Chloride Anhydrous is mixed by 2 ~ 5 mol ratios and inert solvent with isooctyl alcohol, be warming up to 120 ~ 150 DEG C, add phthalic anhydride and tetraethoxysilane in the ratio of magnesium/acid anhydride mol ratio 5 ~ 10, magnesium/silicon mol ratio 20 ~ 50, react and obtain alcohol adduct in 1 ~ 5 hour.
Then according to titanium/magnesium mol ratio 20 ~ 50 alcohol adduct being chilled to room temperature joined in the titanium tetrachloride solution being chilled to-15 ~-40 DEG C in advance, be warming up to 90 ~ 110 DEG C, be 2 ~ 10 add a, b two kinds of diether according to magnesium/total ether mol ratio, the mol ratio of a and b is 0.1 ~ 1,100 ~ 130 DEG C of reactions 1 ~ 3 hour, filter to isolate solid particulate.According to titanium/magnesium mol ratio 20 ~ 50, solid particulate is joined in titanium tetrachloride solution again, stir and 100 ~ 130 DEG C of reactions 1.5 ~ 3 hours, filter to isolate solid particulate.
Finally with the inert solvent washing solid particulate of 50 ~ 80 DEG C, after drying, obtain catalyzer.
Method two: according to the method preparation disclosed in patent CN85100997, first, magnesium compound is dissolved in the solvent system be made up of organic epoxy compound thing, organo phosphorous compounds and inert diluent, mix with titanium compound after forming homogeneous solution, under precipitation additive exists, separate out solids; This solids adopts a, b two kinds of diether compounds to process, make it be attached on solids, if desired, then with titanium tetrahalide and inert diluent, solids is processed, wherein precipitation additive is the one in organic acid anhydride, organic acid, ether, 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.
Described each component is in every mole of magnesium halide, organic epoxy compound thing is 0.2 ~ 10 mole, organo phosphorous compounds is 0.1 ~ 3 mole, precipitation additive is 0 ~ 1.0 mole, titanium compound is 0.5 ~ 150 mole, a, b two kinds of diether compounds amount to 0.02 ~ 0.5 mole, and the mol ratio of a and b is 0.1 ~ 1.
Method three: according to the method Kaolinite Preparation of Catalyst component disclosed in patent CN1091748.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, formation 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 is ball type carrier through washing, drying, and the mol ratio of its alcohol and magnesium chloride is 2 ~ 3, with 2 ~ 2.5 as 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, add a, b two kinds of electron donors in treating processes, the mol ratio of a and b is 0.1 ~ 1, repeatedly wash with inert solvent after process, after drying, obtain the spherical catalyst of solid powdery.The mol ratio of titanium tetrachloride and magnesium chloride is 20 ~ 200, with 30 ~ 60 as well; Initiated process temperature is-30 ~ 0 DEG C, is good with-25 ~-20 DEG C; Final treatment temp is 80 ~ 136 DEG C, is good with 100 ~ 130 DEG C.
Gained spherical catalyst has following feature: titanium content (weight) 1.5% ~ 3.0%, a, b two kinds of ethers add up to content to be 6.0% ~ 20.0%, and cl content 52% ~ 60%, Mg content 10% ~ 20%, inert solvent content 1% ~ 6%, specific surface area of catalyst is greater than 250m
2/ g.
Embodiment 1
In the reactor of fully replacing through high pure nitrogen, add magnesium chloride 4.8g successively, toluene 95ml, epoxy chloropropane 4ml, tributyl phosphate 12.5ml, is warming up to 50 DEG C under stirring, and maintains 2.5 hours, solid dissolves completely, adds Tetra hydro Phthalic anhydride 1.4g, continues maintenance 1 hour.Solution is cooled to less than-25 DEG C, in 1 hour, drips TiCl
456ml, is slowly warming up to 80 DEG C, adds compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 3mmol and 9,9 one two (methyl methoxy base) fluorenes 3mmol, holding temperature 1 hour, after filtration, add toluene 70ml, washing secondary.Add toluene 60ml, TiCl
440ml, is warmed up to 110 DEG C, maintains 2 hours, repeats once.After filtration, add toluene 60ml, washing secondary, obtains solid sediment.Add hexane 60ml again, wash four times.Obtain ingredient of solid catalyst.The catalyst component of above-mentioned preparation is carried out propylene polymerization: volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, add the AlEt of 0.5M
3hexane solution 5ml, Cyclohexylmethyldimethoxysilane (CHMMS) the hexane solution 5ml of 0.02M, then add solid ingredient 8 ~ 10mg and the 1.8NL hydrogen of above-mentioned preparation, pass into liquid propene 2.5L, be warming up to 70 DEG C, maintain this temperature 1 hour, cooling, bleeds off pressure, discharging obtains PP resin, calculate it active, measure degree of isotacticity and the molecular weight distributing index of resulting polymers, concrete outcome is in table 1.
Embodiment 2
With embodiment 1, difference is to be warming up to 80 DEG C, " compound 2-n-pentyl-2-(2-ethylhexyl will be added)-1; 3-Propanal dimethyl acetal 3mmol and 9; 9 one two (methyl methoxy base) fluorenes 3mmol " replace with " add compound 2-n-pentyl-2-(2-ethylhexyl)-1; 3-Propanal dimethyl acetal 2mmol and 9,9 one two (methyl methoxy base) fluorenes 4mmol ", concrete outcome is in table 1.
Embodiment 3
With embodiment 1, difference is to be warming up to 80 DEG C, " compound 2-n-pentyl-2-(2-ethylhexyl will be added)-1; 3-Propanal dimethyl acetal 3mmol and 9; 9 one two (methyl methoxy base) fluorenes 3mmol " replace with " add compound 2-n-pentyl-2-(2-ethylhexyl)-1; 3-Propanal dimethyl acetal 4mmol and 9,9 one two (methyl methoxy base) fluorenes 2mmol, concrete outcome is in table 1.
Embodiment 4
With embodiment 1, difference is to be warming up to 60 DEG C, first adds compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 3mmol, is warming up to 80 DEG C, then adds compound 9,9 one two (methyl methoxy base) fluorenes 4mmol, concrete outcome is in table 1.
Embodiment 5
Under nitrogen protection, 4.8g Magnesium Chloride Anhydrous, 19.5g isooctyl alcohol and 19.5g decane solvent are joined and be equipped with in the 500ml reactor of agitator, be heated to 130 DEG C, reaction 1.5 is little dissolves completely up to magnesium chloride, add 1.1g phthalic anhydride, continue maintenance 130 DEG C reaction and obtain alcohol adduct in 1 hour; Alcohol adduct is cooled to room temperature; Under nitrogen protection; being added drop-wise to by above-mentioned alcohol adduct is chilled in the 120ml titanium tetrachloride solution of-22 DEG C in advance, is slowly warming up to 100 DEG C, adds 2-n-pentyl-2-(2-ethylhexyl)-1; 3-Propanal dimethyl acetal 7mmol; 9,9 one two (methyl methoxy base) fluorenes 3mmol, is warming up to 110 DEG C and maintains 2 hours; filtered while hot; add titanium tetrachloride 120 milliliters, be raised to 110 degree and react 1 hour, filter.With anhydrous hexane solid particulate 4 times, after drying, obtain solid catalyst.The catalyst component of above-mentioned preparation is carried out propylene polymerization: volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, add AlEt32.5mmol, Cyclohexylmethyldimethoxysilane (CHMMS) 0.1mmol, add above-mentioned ingredient of solid catalyst 8-10mg and 1.8NL hydrogen again, pass into liquid propene 2.3L, be warming up to 70 DEG C, maintain this temperature 1 hour.Cooling, pressure release, obtain PP powder, concrete outcome is in table 1.
Embodiment 6
With embodiment 1, add 9.0NL hydrogen when difference is polymerization, concrete outcome is in table 2.
Embodiment 7
With embodiment 5, add 9.0NL hydrogen when difference is polymerization, concrete outcome is in table 2.
Comparative example 1
With embodiment 1, difference is to be warming up to 80 DEG C, adds compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 6mmol, do not add 9,9 one two (methyl methoxy base) fluorenes, concrete outcome is in table 1.
Comparative example 2
With embodiment 1, difference is to be warming up to 80 DEG C, adds compound 9, and 9 one two (methyl methoxy base) fluorenes 6mmol, does not add 2-n-pentyl-2-(2-ethylhexyl)-1,3-dimethoxy the third, concrete outcome is in table 1.
Comparative example 3
With embodiment 6, difference is to be warming up to 100 DEG C, adds compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 6mmol, do not add 9,9 one two (methyl methoxy base) fluorenes, concrete outcome is in table 1.
Comparative example 4
With comparative example 1, add 9.0NL hydrogen when difference is polymerization, concrete outcome is in table 2.
Comparative example 5
With comparative example 3, add 9.0NL hydrogen when difference is polymerization, concrete outcome is in table 2.
Catalyzer and polymer performance under the low density of hydrogen polymerizing condition of table 1
Catalyzer and polymer performance under table 2 high hydrogen concentration polymerizing condition
As can be seen from the data of table 1, catalyst component of the present invention and catalyzer due to the electron donor that have employed a, b two kinds different composite, under the synergy of two kinds of electron donors, the molecular weight distribution of resulting polymers obviously uses b class internal electron donor wide (comparative example 2) than simple, and degree of isotacticity is also than simple increase (comparative example 1 and the comparative example 3) that use a class electron donor, the more important thing is, when improve polymerization time hydrogen concentration time, as can be seen from the data of table 2 we, a class internal electron donor is used if simple, under high hydrogen concentration, the degree of isotacticity of resulting polymers sharply declines (comparative example 4 and comparative example 5), polymkeric substance can be caused to be clamminess, direct consequence causes conversion unit to block exactly, cannot continue to produce, if but adopt a, b two kinds of electron donors are composite, even if under the polymerizing condition of Gao Qing, the degree of isotacticity of resulting polymers still can remain on higher level, meet the demand of suitability for industrialized production, consolidated statement 1, the data of table 2, we can draw catalyst component of the present invention and catalyzer, owing to have employed a, b two kinds of electron donors are composite, under the synergy of two kinds of dissimilar electron donors, catalyzer over-all properties is very superior, remain diether catalyst hydrogen response good while, overcome the simple catalyzer resulting polymers narrow molecular weight distribution using b class electron donor, be unfavorable for post-production, and the defect of developing new product variety and new grades, also successfully overcome the simple a class electron donor catalyst that uses under the polymerizing condition of higher hydrogen gas concentration simultaneously, resulting polymers degree of isotacticity sharply declines, cannot the problem of suitability for industrialized production.
Claims (18)
1., for a catalyst component for olefinic polymerization, it includes the reaction product of magnesium compound, titanium compound and a, b two kind of two ethers electron donor compound,
Electron donor a is selected from the one in the diether compound of following logical formula I:
In formula: R is C
1~ C
10alkyl;
R
1-kind of C
2~ C
7the alkyl of straight or branched, or H in described alkyl is optionally by-individual hybrid atom MCM-41, and described heteroatoms is selected from F, Cl, Br or I;
R
2with R
1difference is C
6~ C
10aryl, C
7~ C
10aralkyl or alkaryl or (R
3r
4)-CH-CH
2-group, wherein R
3, R
4group is identical or different, is selected from C respectively
1~ C
10straight chained alkyl, but R
3with R
4asynchronously CH
3, or R
3with R
4be connected with each other and form H in cycloalkyl or above-mentioned group optionally by-individual hybrid atom MCM-41, described heteroatoms is selected from F, Cl, Br or I;
Electron donor b is selected from the one in the diether compound of following logical formula II:
In logical formula II, R ' is identical or not identical, is selected from the C of hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20cyclophane base, C
7-C
20in aralkyl-kind;
R
1identical or not identical, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20cyclophane base and C
7-C
20in aralkyl-kind;
R
2identical or not identical, be selected from the C of hydrogen, halogen atom, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20cyclophane base and C
7-C
20in aralkyl-kind.
2. the catalyst component for olefinic polymerization according to claim 1, in every mole of magnesium, electron donor compound a add-on is 0.01 ~ 0.5 mole, and the mol ratio of a and b is 0.05 ~ 10.
3. the catalyst component for olefinic polymerization according to claim 1, in every mole of magnesium, electron donor compound a is 0.02 ~ 0.1 mole, and the mol ratio of a and b add-on is 0.1 ~ 1.
4. the catalyst component for olefinic polymerization according to claim 1, in general formula (I), R is methyl or ethyl.
5. the catalyst component for olefinic polymerization according to claim 1, R in general formula (I)
1c
2~ C
7the alkyl of straight or branched.
6. the catalyst component for olefinic polymerization according to claim 1, R in general formula (I)
2phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, Cvclopropvlmethvl or cyclobutylmethyl.
7. the catalyst component for olefinic polymerization according to claim 1, in general formula (I), R is methyl or ethyl, R
1c
2~ C
7the alkyl of straight or branched and R
2phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, Cvclopropvlmethvl or cyclobutylmethyl.
8. the catalyst component for olefinic polymerization according to claim 1, the R in logical formula II
'hydrogen, halogen atom or C
1~ C
6alkyl.
9. the catalyst component for olefinic polymerization according to claim 1, the R in logical formula II
1hydrogen, methyl or ethyl.
10. the catalyst component for olefinic polymerization according to claim 1, the R in logical formula II
2methyl or ethyl.
11. catalyst components for olefinic polymerization according to claim 1, the R in logical formula II
'hydrogen, halogen atom or C
1~ C
6alkyl, R
1hydrogen, methyl or ethyl, R
2methyl or ethyl.
12. catalyst components for olefinic polymerization according to claim 1, in general formula (I), R is methyl or ethyl, R
1c
2~ C
7the alkyl of straight or branched and R
2phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, Cvclopropvlmethvl or cyclobutylmethyl, the R in logical formula II
'hydrogen, halogen atom or C
1~ C
6alkyl, R
1hydrogen, methyl or ethyl, R
2methyl or ethyl.
13. catalyst components for olefinic polymerization according to claim 1, wherein titanium compound is general formula is TiX
i n(OR
i)
4-n, R in formula
ifor carbonatoms is the alkyl of 1 ~ 20, X
ifor halogen, n=1 ~ 4, magnesium compound is selected from magnesium dihalide, the hydrate of alkoxyl Mei ﹑ Wan Ji Mei ﹑ magnesium dihalide or alcohol adduct, and the one in the derivative that in magnesium dihalide molecular formula, one of them halogen atom alkoxy or halogenated alkoxy are replaced, or their mixture.
14. catalyst components for olefinic polymerization according to claim 1, in every mole of magnesium, the content of titanium atom is 0.01 ~ 0.5 mole.
15. catalyst components for olefinic polymerization according to claim 1, in every mole of magnesium, the content of titanium atom is 0.02 ~ 0.1 mole.
16.-kind is used for the catalyzer of olefinic polyreaction, comprises the reaction product of following component:
(1) claim 1 ~ 15 it-described catalyst component;
(2) alkylaluminium cpd;
(3) optionally, external electron donor component.
17.-kind is used for the pre-polymerized catalyst of olefinic polymerization, described pre-polymerized catalyst comprises-prepolymer of prepolymerization gained kind is carried out according to the catalyzer described in claim 16 and alkene, and pre-polymerization multiple is 0.1 ~ 1000g olefin polymer/g ingredient of solid catalyst.
18. 1 kinds of methods for olefinic polymerization, carry out under the catalyzer described in claim 16 or 17 or pre-polymerized catalyst exist.
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Citations (5)
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|---|---|---|---|---|
| US4287328A (en) * | 1978-12-01 | 1981-09-01 | Chisso Corporation | Method for producing α-olefin polymers |
| CN1066274A (en) * | 1991-03-27 | 1992-11-18 | 希蒙特公司 | Components and catalysts for the polymerization of olefins |
| CN1143651A (en) * | 1995-02-21 | 1997-02-26 | 蒙特尔北美公司 | Components and catalysts for the polymerization of olefins |
| CN1298887A (en) * | 1999-12-06 | 2001-06-13 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| CN1436796A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Solid catalyst component for olefine polymerization, catalyst with the component and its application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6010525B2 (en) * | 1978-03-22 | 1985-03-18 | 旭化成株式会社 | Catalyst for polyolefin production |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287328A (en) * | 1978-12-01 | 1981-09-01 | Chisso Corporation | Method for producing α-olefin polymers |
| CN1066274A (en) * | 1991-03-27 | 1992-11-18 | 希蒙特公司 | Components and catalysts for the polymerization of olefins |
| CN1143651A (en) * | 1995-02-21 | 1997-02-26 | 蒙特尔北美公司 | Components and catalysts for the polymerization of olefins |
| CN1298887A (en) * | 1999-12-06 | 2001-06-13 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| CN1436796A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Solid catalyst component for olefine polymerization, catalyst with the component and its application |
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