CN103626893A - Catalyst component for alkene polymerization reactions and preparation method of catalyst prepared from the catalyst component - Google Patents
Catalyst component for alkene polymerization reactions and preparation method of catalyst prepared from the catalyst component Download PDFInfo
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Abstract
The invention provides a catalyst component for alkene polymerization reactions and a preparation method of a catalyst prepared from the catalyst component. The catalyst component comprises a magnesium compound, a titanium compound, and a reaction product of two diether electron donor compounds a and b. When the catalyst is applied to propylene polymerization, a satisfactory polymerization yield can be obtained, furthermore the polymer obtained has the advantages of high isotacticity, wide molecular weight distribution range, and good sensitivity to hydrogen, and even under a polymerization condition of high hydrogen gas concentration, the isotacticity of the polymer can still be maintained in a high level, and thus the requirement of the industrial production is satisfied.
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 of doing internal electron donor of electron donor.
Technical background
As everyone knows, using magnesium, titanium, halogen and the electron donor solid titanium catalyst component as basal component, can be used for olefinic polyreaction, particularly at the alpha-olefine polymerizing with 3 carbon or more carbon atoms, 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, comparatively conventional is aromatic carboxylates's class of binary, and such as n-butyl phthalate or diisobutyl phthalate etc., as Chinese patent CN85100997A.
In recent years, people attempt again to adopt other compound, as diether, as the electron donor in olefin polymerization catalyst components, use, for example the disclosed catalyst component for olefinic polyreaction of Chinese patent CN96107325.X and CN89107675.1, has adopted 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1, the diether compounds such as 3-Propanal dimethyl acetal and 9,9-bis-(methoxymethyl) fluorenes are as electron donor.Yet above-mentioned disclosed to using catalyzer ubiquity molecular weight distribution in the practical application of olefinic polymerization that diether compound prepared as internal electron donor narrow, unmanageable defect, the disclosed catalyst component for olefinic polyreaction of Chinese patent CN102040485 and CN102040684, adopted 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 molecular weight distribution that can broadening polymkeric substance in the practical application of olefinic polymerization with this type of catalyzer, but in polymerization process, the concentration of hydrogen when improving polymerization, can cause the degree of isotacticity of polymkeric substance sharply to decline, not only cannot utilize preferably the concentration of hydrogen to regulate the molecular weight of final polymkeric substance, also easily cause the obstruction of conversion unit, be difficult to realize suitability for industrialized production.
The 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, the advantage that has not only retained 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, has solved the technical barrier that above-mentioned two ethers catalyzer run in process of production.
Summary of the invention
One of the object of the invention has been to provide a kind of catalyst component for olefinic polymerization, the reaction product that comprises magnesium compound, titanium compound and a, two kind of two ethers electron donor compound of b,
Electron donor a is selected from a kind of 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 optionally replaces by a heteroatoms, 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 respectively C
1～C
10straight chained alkyl, but R
3with R
4when different, are CH
3, or R
3with R
4h in formation cycloalkyl connected with each other or above-mentioned group is optionally replaced by a heteroatoms, and described heteroatoms is selected from F, Cl, Br or I; Be preferably phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, cyclopropyl methyl or cyclobutylmethyl.
The example of the suitable compound of electron donor a 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-cyclopropyl methyl isophthalic acid, 3-Propanal dimethyl acetal, 2-propyl group-2-cyclopropyl methyl isophthalic acid, 3-Propanal dimethyl acetal, 2-normal-butyl-2-cyclopropyl methyl isophthalic acid, 3-Propanal dimethyl acetal, 2-n-pentyl-2-cyclopropyl methyl isophthalic acid, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclopropyl methyl isophthalic acid, 3-Propanal dimethyl acetal, 2-isobutyl--2-cyclopropyl methyl isophthalic acid, 3-Propanal dimethyl acetal, 2-isopentyl-2-cyclopropyl methyl isophthalic acid, 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-cyclopropyl methyl isophthalic acid, 3-Propanal dimethyl acetal, 2-isopentyl-2-cyclopropyl methyl isophthalic acid, 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 a kind of 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
20a kind of 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
20a kind of 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
20a kind of in aralkyl, is preferably methyl or ethyl.
The example of the suitable compound of electron donor b includes but not limited to:
Two (methoxymethyl) indenes of 1,1-, two (methoxymethyl)-2 of 1,1-, 3-dimethoxy indenes, two (methoxyl group-methyl)-4,5,6 of 1,1-, 7-tetrafluoro indenes, two (methoxymethyl)-2,3,6 of 1,1-, 7-tetrafluoro indenes, two (methoxymethyl)-4,7 of 1,1-dimethyl indenes, two (methoxymethyl)-3,6 of 1,1-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 propyl) indenes of 1,1-, two (the methoxymethyl)-7-trimethyl silyl indenes of 1,1-, two (the methoxymethyl)-7-trifluoromethyl indenes of 1,1-, two (methoxymethyl)-4,7 of 1,1-dimethyl 4,5,6,7-tetrahydroindene, two (methoxymethyl)-7 of 1,1-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-, two (methoxymethyl)-7 of 1,1-tertiary butyl indenes, two (methoxymethyl)-7 of 1, the 1-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-, two (methoxymethyl)-2,3,6 of 9,9-, 7-tetramethyl-fluorenes, two (methoxymethyl)-2,3,4,5,6 of 9,9-, 7-hexafluoro fluorenes, two (methoxymethyl)-2 of 9,9-, 3-phenylpropyl alcohol indenes, two (methoxymethyl)-2,3,6 of 9,9-, 7-bis-phenylpropyl alcohol indenes, two (methoxymethyl)-2 of 9,9-, 7-bis-cyclopentyl fluorenes, two (methoxymethyl)-1 of 9,9-, 8-dichloro fluorenes, two (methoxymethyl)-2 of 9,9-, 7-bis-cyclopentyl fluorenes, two (methoxymethyl)-1 of 9,9-, 8-difluoro fluorenes, two (methoxymethyl)-1,2,3 of 9,9-, 4-tetrahydrochysene fluorenes, two (methoxymethyl)-1,2,3,4,5,6,7 of 9,9-, 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-, two (the 1'-methoxy ethyls)-5 of 1,1-, 6-dichloro indenes, two (phenoxymethyl)-3 of 1,1-, 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 (the 1'-isopropoxy-normal-butyls)-4 of 9,9-, 5-diphenylfluorene, 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 naphthalenes of 1,1-, two (methoxymethyl)-Isosorbide-5-Nitrae-methane dihydronaphthalene of 9,9-, 9,9-pair-(methoxymethyl)-9,10-dihydroanthracene, 1,1-pair-(methoxymethyl)-1,2-dihydroanthracene, two (the methoxymethyl)-1-phenyl-Isosorbide-5-Nitrae-dihydronaphthalene of 4,4-, two (the methoxymethyl)-1-of 4,4-phenyl-3,4-dihydronaphthalene.
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; Preferably 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 guarantee that final resulting polymers has higher degree of isotacticity, R is methyl or ethyl, R in the preferred self-drifting of electron donor compound a (I)
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, cyclopropyl methyl 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 is selected from a kind of in the derivative that one of them halogen atom in the hydrate of magnesium dihalide, magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula replaced by-oxyl or halo-oxyl, or their mixture, preferred magnesium dihalide, for example magnesium dichloride, dibrominated magnesium, two magnesium iodides.
It is TiX that titanium compound used can be selected general formula
i n(OR
i)
4-ncompound, R in formula
ifor carbonatoms be 1～20 alkyl, X
ifor halogen, n=1～4.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.
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, the reaction product that comprises following component:
(1) above-mentioned catalyst component
(2) alkylaluminium cpd;
(3) optionally, external electron donor component.
Wherein alkylaluminium cpd is that general formula is AlR
iI nx
iI 3-ncompound, R in formula
iIfor hydrogen, the alkyl that carbonatoms is 1～20, X
iIfor halogen, the number that n is 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 ethyl aluminum chloride, ethyl aluminum dichloride, preferably triethyl aluminum, triisobutyl aluminium.
When needing the application of the very high olefin polymer of taxis, need add (3) external donor compound, for example 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 can be also halogen or 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.
The ratio between component (1), component (2) and component (3) wherein, take 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 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., wherein alkene is selected from ethene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene, the equal polymerization of special propylene with or the copolymerization of other alkene of propylene, be to adopt following reaction conditions preferably:
Polymerization temperature: 0～150 ℃, preferably 60～90 ℃.
Catalyzer of the present invention can directly add in reactor for polymerization process, or catalyzer can carry out prepolymerization before adding first polymerization reactor, in the present invention, term " pre-polymerized catalyst " means the catalyzer through polymerization procedure with lower transforming degree.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.
Can adopt the alpha-olefin identical with aforementioned alkene to carry out prepolymerization, wherein carry out prepolymerized alkene and be preferably ethene or propylene, specifically, particularly preferably be, the mixture that adopts 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 approximately 0.2 gram to approximately 500 grams polymkeric substance/gram ingredient of solid catalyst.
Prepolymerization operation can be at-20 to 80 ℃, preferably at the temperature of 0～50 ℃, in liquid or in gas phase, carry out, the part that prepolymerization step can be used as in continuous polymerization technique is carried out online, or carry 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 propylene particularly preferably, 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 use the diether compound of two kinds of different structures as electron donor simultaneously, can obtain the catalyzer of high comprehensive performance, catalyzer not only active high, hydrogen response good, the molecular weight distribution of resulting polymers is wide simultaneously, the post-production and the new product grade of exploitation that are conducive to polymkeric substance, even under the polymerizing condition of high hydrogen concentration, resulting polymers degree of isotacticity is still higher, has met demand of industrial production.
Embodiment
Embodiment given below is for the present invention is described, rather than 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 use the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to constant weight gained is degree of isotacticity with 2 ratio.
2, molecular weight distribution: use PL-GPC 220 to measure.
3, melting index MFI measures according to ASTM D1238-99.
Catalyst component preparation method:
Can select diverse ways to prepare ingredient of solid catalyst of the present invention, just enumerate the method for several Kaolinite Preparation of Catalysts below, rather than the preparation of catalyzer involved in the present invention is defined in to this.
Method one: as according to the disclosed method Kaolinite Preparation of Catalyst of 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 ℃, in the ratio of magnesium/acid anhydride mol ratio 5～10, magnesium/silicon mol ratio 20～50, add phthalic anhydride and tetraethoxysilane, react and within 1～5 hour, obtain alcohol adduct.
Then according to titanium/magnesium mol ratio 20～50, the alcohol adduct that is chilled to room temperature is joined in advance in the titanium tetrachloride solution that is chilled to-15～-40 ℃, be warming up to 90～110 ℃, according to magnesium/total ether mol ratio, be 2～10 to add a, two kinds of diether of b, the mol ratio of a and b is 0.1～1,100～130 ℃ of reactions 1～3 hour, filter to isolate solid particulate.According to titanium/magnesium mol ratio 20～50, solid particulate is joined in titanium tetrachloride 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 catalyzer.
Method two: according to the disclosed method preparation of patent CN85100997, first, magnesium compound is dissolved in the solvent system being formed by organic epoxy compounds, organo phosphorous compounds and inert diluent, after forming homogeneous solution, mix with titanium compound, under precipitation additive exists, separate out solids; This solids by using a, two kinds of diether compounds of b are processed, it is attached on solids, if desired, then with titanium tetrahalide and inert diluent, solids is processed, wherein precipitation additive is a kind of 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 compounds 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, two kinds of diether compounds of b amount to 0.02 ~ 0.5 mole, and the mol ratio of a and b is 0.1～1.
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, add a, two kinds of electron donors of b in treating processes, the mol ratio of a and b is 0.1～1, after processing, with inert solvent, repeatedly wash, after being dried, obtain the spherical catalyst 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.
Gained spherical catalyst has following feature: titanium content (weight) 1.5%～3.0%, and it is 6.0%～20.0% that a, two kinds of ethers of b add up to content, 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 successively magnesium chloride 4.8g, toluene 95ml, epoxy chloropropane 4ml, tributyl phosphate 12.5ml, is warming up to 50 ℃, and maintains 2.5 hours under stirring, solid dissolves completely, adds Tetra hydro Phthalic anhydride 1.4g, continues to maintain 1 hour.Solution is cooled to below-25 ℃, in 1 hour, drips TiCl
456ml, is slowly warming up to 80 ℃, 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 ℃, maintains 2 hours, repeats once.After filtration, add toluene 60ml, washing secondary, obtains solid sediment.Add again hexane 60ml, wash four times.Obtain ingredient of solid catalyst.The catalyst component of above-mentioned preparation is carried out to propylene polymerization: the stainless steel cauldron that volume is 5L, after gaseous propylene is fully replaced, adds the AlEt of 0.5M
3hexane solution 5ml, the Cyclohexylmethyldimethoxysilane of 0.02M (CHMMS) hexane solution 5ml, 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 ℃, maintain this temperature 1 hour, cooling, bleeds off pressure, discharging obtains PP resin, calculate its activity, 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 ℃, to " add compound 2-n-pentyl-2-(2-ethylhexyl)-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 ℃, to " add compound 2-n-pentyl-2-(2-ethylhexyl)-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 ℃, first adds compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 3mmol, is warming up to 80 ℃, 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 in the 500ml reactor that agitator is housed, be heated to 130 ℃, react and dissolve completely to magnesium chloride for 1.5 hours, add 1.1g phthalic anhydride, continue to maintain 130 ℃ of reactions and within 1 hour, obtain alcohol adduct; Alcohol adduct is cooled to room temperature; Under nitrogen protection; above-mentioned alcohol adduct is added drop-wise in advance in the 120ml titanium tetrachloride solution that is chilled to-22 ℃, is slowly warming up to 100 ℃, add 2-n-pentyl-2-(2-ethylhexyl)-1; 3-Propanal dimethyl acetal 7mmol; 9,9 one two (methyl methoxy base) fluorenes 3mmol, are warming up to 110 ℃ and maintain 2 hours; filtered while hot; add 120 milliliters of titanium tetrachlorides, be raised to 110 degree reaction 1 hour, filter.With anhydrous hexane solid particulate 4 times, obtain solid catalyst after dry.The catalyst component of above-mentioned preparation is carried out to propylene polymerization: the stainless steel cauldron that volume is 5L, after gaseous propylene is fully replaced, add AlEt32.5mmol, Cyclohexylmethyldimethoxysilane (CHMMS) 0.1mmol, add again above-mentioned ingredient of solid catalyst 8-10mg and 1.8NL hydrogen, pass into liquid propene 2.3L, be warming up to 70 ℃, maintain this temperature 1 hour.Cooling, pressure release, obtains PP powder, and concrete outcome is in Table 1.
Embodiment 6
With embodiment 1, when being polymerization, difference adds 9.0NL hydrogen, and concrete outcome is in Table 2.
Embodiment 7
With embodiment 5, when being polymerization, difference adds 9.0NL hydrogen, and concrete outcome is in Table 2.
Comparative example 1
With embodiment 1, difference is to be warming up to 80 ℃, adds compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 6mmol, does not add 9,9 one two (methyl methoxy base) fluorenes, and concrete outcome is in Table 1.
Comparative example 2
With embodiment 1, difference is to be warming up to 80 ℃, adds compound 9,9 one or 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 ℃, adds compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 6mmol, does not add 9,9 one two (methyl methoxy base) fluorenes, and concrete outcome is in Table 1.
Comparative example 4
With comparative example 1, when being polymerization, difference adds 9.0NL hydrogen, and concrete outcome is in Table 2.
Comparative example 5
With comparative example 3, when being polymerization, difference adds 9.0NL hydrogen, and 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
From the data of table 1, can find out, catalyst component of the present invention and catalyzer are owing to having adopted a, two kinds of different electron donors of b composite, under the synergy of two kinds of electron donors, the molecular weight distribution of resulting polymers is obviously than the simple b class internal electron donor wide (comparative example 2) that uses, and degree of isotacticity is also than increase (comparative example 1 and the comparative example 3) of simple use a class electron donor, the more important thing is, when improving polymerization during the concentration of hydrogen, from the data of table 2, we can find out, if use merely a class internal electron donor, under high hydrogen concentration, the degree of isotacticity of resulting polymers sharply decline (comparative example 4 and comparative example 5), can cause polymkeric substance to be clamminess, directly consequence causes conversion unit to stop up exactly, cannot continue to produce, if but adopt a, two kinds of electron donors of b are composite, even under the polymerizing condition of Gao Qing, the degree of isotacticity of resulting polymers still can remain on higher level, met 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 having adopted a, two kinds of electron donors of b are composite, under the synergy of two kinds of dissimilar electron donors, catalyzer over-all properties is very superior, retained diether catalyst hydrogen response good in, overcome the catalyzer resulting polymers narrow molecular weight distribution of simple use b class electron donor, be unfavorable for post-production, and the defect of developing new product variety and the new trade mark, also successfully overcome simple use a class electron donor catalyst under the polymerizing condition of higher hydrogen gas concentration simultaneously, resulting polymers degree of isotacticity sharply declines, problem that cannot 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, two kind of two ethers electron donor compound of b,
Electron donor a is selected from a kind of in the diether compound of following logical formula I:
In formula: R is C
1～C
10alkyl;
R
1a kind of C
2～C
7the alkyl of straight or branched, or the H in described alkyl optionally replaces by a heteroatoms, 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 respectively C
1～C
10straight chained alkyl, but R
3with R
4when different, are CH
3, or R
3with R
4h in formation cycloalkyl connected with each other or above-mentioned group is optionally replaced by a heteroatoms, and described heteroatoms is selected from F, Cl, Br or I;
Electron donor b is selected from a kind of in the diether compound of following logical formula II:
（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
20a kind of in aralkyl;
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
20a kind of in aralkyl;
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
20a kind of in aralkyl.
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, 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, the mol ratio of a and b add-on is 0.1～1.
4. the catalyst component for olefinic polyreaction according to claim 1, in general formula (I), R is methyl or ethyl.
5. the catalyst component for olefinic polyreaction according to claim 1, R in general formula (I)
1c
2～C
7the alkyl of straight or branched.
6. the catalyst component for olefinic polyreaction according to claim 1, R in general formula (I)
2phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, cyclopropyl methyl or cyclobutylmethyl.
7. the catalyst component for olefinic polyreaction 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, cyclopropyl methyl or cyclobutylmethyl.
8. the catalyst component for olefinic polyreaction according to claim 1, the R ' in logical formula II is hydrogen, halogen atom or C
1～C
6alkyl.
9. the catalyst component for olefinic polyreaction according to claim 1, leads to the R in formula II
1hydrogen, methyl or ethyl.
10. the catalyst component for olefinic polyreaction according to claim 1, leads to the R in formula II
2methyl or ethyl.
11. catalyst components for olefinic polyreaction according to claim 1, the R ' in logical formula II is hydrogen, halogen atom or C
1～C
6alkyl, R
1hydrogen, methyl or ethyl, R
2methyl or ethyl.
12. catalyst components for olefinic polyreaction according to claim 1, R is methyl or ethyl, R in general formula (I)
1c
2～C
7the alkyl of straight or branched and R
2be phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, cyclopropyl methyl or cyclobutylmethyl, the R ' in logical formula II is hydrogen, halogen atom or C
1～C
6alkyl, R
1hydrogen, methyl or ethyl, R
2methyl or ethyl.
13. catalyst components for olefinic polyreaction according to claim 1, wherein titanium compound is that general formula is TiX
in (OR
i)
4-n, R in formula
ifor carbonatoms be 1～20 alkyl, X
ifor halogen, n=1～4, magnesium compound is selected from hydrate or the alcohol adduct of magnesium dihalide, alkoxyl Mei ﹑ Wan Ji Mei ﹑ magnesium dihalide, and a kind of 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. 1 kinds of catalyzer for olefinic polyreaction, the reaction product that comprises following component:
(1) the described catalyst component of one of claim 1～15;
(2) alkylaluminium cpd;
(3) optionally, external electron donor component.
17. 1 kinds of pre-polymerized catalysts for olefinic polymerization, described pre-polymerized catalyst comprises a kind of prepolymer that carries out prepolymerization gained 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 are carried out under the catalyzer described in claim 16 or 17 or pre-polymerized catalyst existence.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171195A (en) * | 2018-11-13 | 2020-05-19 | 韩华道达尔有限公司 | Propylene polymerization solid catalyst for reducing VOC and method for producing polypropylene using the same |
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