CN103626895A - Catalyst component for alkene polymerization reactions and preparation method of catalyst thereof - Google Patents
Catalyst component for alkene polymerization reactions and preparation method of catalyst thereof Download PDFInfo
- Publication number
- CN103626895A CN103626895A CN201210303463.6A CN201210303463A CN103626895A CN 103626895 A CN103626895 A CN 103626895A CN 201210303463 A CN201210303463 A CN 201210303463A CN 103626895 A CN103626895 A CN 103626895A
- Authority
- CN
- China
- Prior art keywords
- compound
- methyl
- alkyl
- ethyl
- catalyst component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a catalyst component for alkene polymerization reactions and a catalyst thereof. The catalyst component is prepared through the following steps: (1) mixing a magnesium compound with organic alcoholic compounds and an inert solvent, adding a precipitation assisting agent to carry out reactions; (2) contacting the alcoholic adduct obtained in the step (1) with a titanium compound solution at a low temperature, adding electron donor compounds a and b to carry out reactions, filtering so as to obtain solid particles; (3) adding the solid particles into a titanium compound solution, stirring to carry out reactions, filtering so as to obtain solid particles; (4) washing the solid particles with an inert solvent, and drying so as to obtain the catalyst component. 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 polymer can still be maintained in a high level and meets the requirement on industrial production.
Description
Technical field
The present invention relates to-kind of olefin polymerization catalyst components and the method for preparing described catalyzer, be more particularly to-kind by two kinds of composite olefin polymerization catalyst components and application thereof of doing internal electron donor of electron donor compound.
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 at the alpha-olefine polymerizing with 3 carbon or more carbon atoms, wherein electron donor compound be in catalyst component requisite one-tenth divide it-, 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, adopted 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal and 9,9-bis-(methoxymethyl) fluorenes etc. 1,3-diether compound is as electron donor.Yet, the above-mentioned disclosed catalyzer narrow defect of ubiquity molecular weight distribution in the practical application of olefinic polymerization that diether compound prepared as internal electron donor of usining, the disclosed catalyst component for olefinic polyreaction of Chinese patent CN102040485A and CN102040684A, 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 good advantage of hydrogen response that has not only retained two ethers 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 into when suitability for industrialized production is applied.
Summary of the invention
The invention provides a kind of catalyst component for olefinic polymerization, prepared by its method by following step:
(1) magnesium compound and organic alcohol compound and inert solvent are mixed to form to solution;
(2) solution step (1) being obtained contacts with under titanium compound low temperature, under precipitation additive exists, separates out solids; In separating out solids process or separate out after solids, add electron donor compound a and b to react, filter to isolate solid particulate; Described electron donor compound a is selected from least one in the diether compound as shown in logical formula I; Described electron donor compound b is selected from least one in the diether compound shown in logical formula II,
The diether compound structure of described logical formula I is as follows:
In formula: R is C
1～C
10alkyl, preferably methyl, ethyl;
R
1be-kind of C
2～C
7the alkyl of straight or branched, or H wherein optionally replaces by-individual 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, 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-individual heteroatoms, and described heteroatoms is selected from F, Cl, Br or I; R
2be 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.
The diether compound structure of described logical formula II is as follows:
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, 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
20in aralkyl-kind, 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
20in aralkyl-kind, be 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.
(3), by after solid particulate and compound titanium solution contact reacts, after filtering, wash, being dried, obtain catalyst component.
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, R
2it is the compound of phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, cyclopropyl methyl or cyclobutylmethyl; 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.
In step (1), described magnesium compound is selected from the derivative that wherein-individual halogen atom in the hydrate of magnesium dihalide, magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula replaced by-oxyl or halo-oxyl-kind, or their mixture, preferred magnesium dihalide, for example magnesium dichloride, dibrominated magnesium, two magnesium iodides; Described organic alcohol compound is C
2~ C
8monohydroxy-alcohol, be preferably C
6~ C
8monohydroxy-alcohol; Described inert solvent is C
1~ C
20alkane, naphthenic hydrocarbon or aromatic hydrocarbons in a kind of or its mixture.
The general formula of the titanium compound of step (2) is TiX
i n(OR
i)
4-n, R in formula
ifor carbonatoms be 1～20 alkyl, X
ifor halogen, n=1～4; Described precipitation additive is a kind of in organic acid anhydride, organic acid, ether, ketone, alcohol ester, or their mixture.
In above-mentioned catalyst component, in described step (1), preferably magnesium compound and organic alcohol compound are mixed to form to solution by 2～5 mol ratios and inert solvent, be warming up to 120～150 ℃, by magnesium/precipitation additive mol ratio 5～10, add precipitation additive, react 1～5 hour.
In above-mentioned catalyst component, in described step (2), according to titanium/magnesium mol ratio 20～50, the alcohol adduct solution of magnesium is contacted under the cold condition of-15～-40 ℃ with compound titanium solution, be warming up to 90～110 ℃, in separating out solids process or separate out after solids, add electron donor compound a and b to react, in every mole of magnesium, electron donor compound a is 0.01 ~ 0.5 mole, electron donor compound a and b mol ratio are 0.05～10, in order to guarantee that final resulting polymers can have higher degree of isotacticity, preferably electron donor compound a is 0.02 ~ 0.1 mole, the mol ratio of a and b is 0.1～1, 100～130 ℃ of reactions 1～3 hour, filter to isolate solid particulate.
In above-mentioned catalyst component preparation method, in described step (3), preferably according to titanium/magnesium mol ratio 20～50, solid particulate is joined in compound titanium solution, stir and 100～130 ℃ of reactions 1.5～3 hours, filter to isolate solid particulate.
The present invention also provides a kind of catalyzer for olefinic polymerization, the reaction product that comprises following component:
A. the catalyst component of the present invention that prepared by aforesaid method;
B. organo-aluminium compound;
C. inessential component silicoorganic compound.
A (with Ti content meter): B:C=1 mole: 20～800 moles: 0～100 mole wherein
In above-mentioned catalyzer, it is AlR that described organo-aluminium compound is selected from general formula
iInX
iI 3-ncompound at least one, in formula, R is selected from least one in the alkyl of hydrogen, C1 ~ C20; X is halogen; N is the integer of 0<n≤3.Concrete example comprises: the aluminum alkyl halides such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, dichloro one aluminium triethyl, ethyl aluminum dichloride; Wherein preferably triethyl aluminum, triisobutyl aluminium.
In above-mentioned catalyzer, in order to obtain the olefin polymer of very high taxis, need add external donor compound, if general formula is R
iIInSi (OR
iV)
4-nsilicoorganic compound, 0≤n≤3 in formula, R
iIIand R
iVfor of the same race or different alkyl, cycloalkyl, aryl, halogen are for alkane base ﹑ amido, R can be also halogen or hydrogen atom.Concrete example comprises: trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, cyclohexyl methyl diethoxy silane, Cyclohexylmethyldimethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, the silicoorganic compound such as vinyltrimethoxy silane, preferably Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane.
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.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 the-individual 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, adopt propylene or other and propylene mol ratio be up to 20%-kind or the mixture of multiple alpha-olefin carry 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, at-20 to 80 ℃, preferably, at the temperature of 0～50 ℃, be carried out in liquid or in gas phase.Can be used as in continuous polymerization technique-part of prepolymerization step is carried out online, or is carried 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 the requirement of suitability for industrialized 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.
Embodiment 1
(1) preparation of catalyst solid constituent
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 5mmol; 9,9 one two (methyl methoxy base) fluorenes 5mmol, 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.
(2) propylene polymerization
Volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, add AlEt32.5mmol, Cyclohexylmethyldimethoxysilane (CHMMS) 0.l mmol, 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 2
With embodiment 1, difference is to be warming up to 100 ℃, to " add 2-n-pentyl-2-(2-ethylhexyl)-1; 3-Propanal dimethyl acetal 5mmol; 9,9 one two (methyl methoxy base) fluorenes 5mmol " replace with " add compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 3mmol and 9; 9 one two (methyl methoxy base) fluorenes 7mmol ", concrete outcome is in Table 1.
Embodiment 3
With embodiment 1, difference is to be warming up to 100 ℃, to " add 2-n-pentyl-2-(2-ethylhexyl)-1; 3-Propanal dimethyl acetal 5mmol; 9,9 one two (methyl methoxy base) fluorenes 5mmol " replace with " add compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 7mmol and 9; 9 one two (methyl methoxy base) fluorenes 3mmol ", concrete outcome is in Table 1.
Embodiment 4
With embodiment 1, when difference is to be first warming up to 80 ℃, add compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 5mmol, then be warming up to 100 ℃, add compound 9,9 one two (methyl methoxy base) fluorenes 5mmol, concrete outcome is in Table 1.
Embodiment 5
With embodiment 1, when being polymerization, difference adds 9.0NL hydrogen, and concrete outcome is in Table 2.Embodiment 6
With embodiment 2, 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 100 ℃, to " add 2-n-pentyl-2-(2-ethylhexyl)-1; 3-Propanal dimethyl acetal 5mmol; 9; 9 one two (methyl methoxy base) fluorenes 5mmol " replace with " add compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 6mmol ", concrete outcome is in Table 1.
Comparative example 2
With embodiment 1, difference is to be warming up to 100 ℃, to " add 2-n-pentyl-2-(2-ethylhexyl)-1; 3-Propanal dimethyl acetal 5mmol; 9; 9 one two (methyl methoxy base) fluorenes 5mmol " replace with " adding compound 9,9 one or two (methyl methoxy base) fluorenes 6mmol ", concrete outcome is in Table 1.
Comparative example 3
With comparative example 1, 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 wide than the simple b class internal electron donor (comparative example 2) that uses, and degree of isotacticity is increasing than simple use a class electron donor (comparative example 1) also, 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 (comparative example 3), under high hydrogen concentration, the degree of isotacticity of resulting polymers sharply declines, 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 (17)
1. for a catalyst component for olefinic polymerization, prepared by its method by following step:
(1) magnesium compound and organic alcohol compound and inert solvent are mixed to form to solution;
(2) solution step (1) being obtained contacts with under titanium compound low temperature, under precipitation additive exists, separates out solids; In separating out solids process or separate out after solids, add electron donor compound a and b to react, filter to isolate solid particulate;
Described electron donor compound a is selected from least one in the diether compound as shown in logical formula I; Described electron donor compound b is selected from least one in the diether compound shown in logical formula II;
The diether compound structure of described logical formula I is as follows:
In formula: R is C
1～C
10alkyl;
R
1be-kind of C
2～C
7the alkyl of straight or branched, or the H in described alkyl optionally replaces by-individual 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-individual heteroatoms, and described heteroatoms is selected from F, Cl, Br or I;
The diether compound structure of described logical formula II is as follows:
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, 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, C
7-C
20in aralkyl-kind;
(3), by after solid particulate and titanium compound contact reacts, after filtering, wash, being dried, obtain catalyst component.
2. according to claim 1 for the catalyst component of olefinic polymerization, in step (2), 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 polyreaction according to claim 1, in step (2), in every mole of magnesium, electron donor compound a add-on is 0.02～0.1 mole, the mol ratio of a and b is 0.1～1.
4. the catalyst component for olefinic polyreaction according to claim 1, in step (2), a and b can add simultaneously, also can at differential responses temperature, add.
5. the catalyst component for olefinic polyreaction according to claim 1, in the diether compounds of the described general formula of step (2) (I), R is methyl or ethyl.
6. the catalyst component for olefinic polyreaction according to claim 1, in the diether compounds of the described general formula of step (2) (I), R
1c
2～C
7the alkyl of straight or branched.
7. the catalyst component for olefinic polyreaction according to claim 1, in the diether compounds of the described general formula of step (2) (I), 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, in the diether compounds of the general formula (I) described in step (2), 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.
9. the catalyst component for olefinic polyreaction according to claim 1, in the diether compounds of the logical formula II described in step (2), R ' is hydrogen, halogen atom or C
1～C
6alkyl.
10. the catalyst component for olefinic polyreaction according to claim 1, in the diether compounds of the logical formula II described in step (2), R
1hydrogen, methyl or ethyl.
11. catalyst components for olefinic polyreaction according to claim 1, in the diether compounds of the logical formula II described in step (2), R
2methyl or ethyl.
12. catalyst components for olefinic polyreaction according to claim 1, in the diether compounds of the logical formula II described in step (2), R ' 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, in the diether compounds of the general formula (I) described in step (2), R is methyl or ethyl, R
1c
1～C
7the alkyl of straight or branched and R
2phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, cyclopropyl methyl or cyclobutylmethyl; In the diether compounds of logical formula II, R ' is hydrogen, halogen atom or C
1～C
6alkyl, R
1hydrogen, methyl or ethyl, R
2methyl or ethyl.
14. catalyst components for olefinic polyreaction according to claim 1, magnesium compound described in step (1) is a kind of in the derivative that in the hydrate of magnesium dihalide, magnesium dihalide or alcohol adduct or magnesium dihalide molecular formula, one of them halogen atom is replaced by-oxyl or halo-oxyl; Described organic alcohol compound is C
2~ C
8monohydroxy-alcohol; Described inert solvent is C
1~ C
20alkane, naphthenic hydrocarbon or aromatic hydrocarbons in a kind of or its mixture; The general formula of the titanium compound of step (2) is TiX
i n(OR
i)
4-n, R in formula
ifor carbonatoms be 1～20 alkyl, X
ifor halogen, n=1～4; Described precipitation additive is a kind of in organic acid anhydride, organic acid, ether, ketone, alcohol ester, or their mixture.
15. catalyst components for olefinic polyreaction according to claim 1, in step (1), the mol ratio of magnesium compound and Organic Alcohol is 2～5.
16. catalyst components for olefinic polyreaction according to claim 1, in step (2), the add-on of magnesium compound and titanium compound is 20～50 by the molar ratio computing of titanium/magnesium; The mol ratio of magnesium compound and precipitation additive is 5～10.
17.-kind is for CH
2the catalyzer of=CHR olefinic polyreaction, wherein R is hydrogen or C
1～C
6alkyl or aryl, the reaction product that comprises following component:
(1) claim 1～16 it-described catalyst component;
(2) alkylaluminium cpd;
(3) optionally, external electron donor component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210303463.6A CN103626895B (en) | 2012-08-23 | 2012-08-23 | For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210303463.6A CN103626895B (en) | 2012-08-23 | 2012-08-23 | For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103626895A true CN103626895A (en) | 2014-03-12 |
| CN103626895B CN103626895B (en) | 2016-03-30 |
Family
ID=50208369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210303463.6A Active CN103626895B (en) | 2012-08-23 | 2012-08-23 | For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103626895B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107840909A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of ingredient of solid catalyst, catalyst system and pre-polymerized catalyst for olefinic polymerization |
| CN113136239A (en) * | 2020-01-19 | 2021-07-20 | 清华大学 | Utilization method of ethylene cracking tar and application of compound containing carbon-carbon double bond |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54124887A (en) * | 1978-03-22 | 1979-09-28 | Asahi Chem Ind Co Ltd | Catalyst for preparing polyolenin |
| 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 | The component and the catalyzer that are used for olefinic polyreaction |
| CN1143651A (en) * | 1995-02-21 | 1997-02-26 | 蒙特尔北美公司 | Component and catalysts for 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 |
-
2012
- 2012-08-23 CN CN201210303463.6A patent/CN103626895B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54124887A (en) * | 1978-03-22 | 1979-09-28 | Asahi Chem Ind Co Ltd | Catalyst for preparing polyolenin |
| 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 | The component and the catalyzer that are used for olefinic polyreaction |
| CN1143651A (en) * | 1995-02-21 | 1997-02-26 | 蒙特尔北美公司 | Component and catalysts for 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107840909A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of ingredient of solid catalyst, catalyst system and pre-polymerized catalyst for olefinic polymerization |
| CN113136239A (en) * | 2020-01-19 | 2021-07-20 | 清华大学 | Utilization method of ethylene cracking tar and application of compound containing carbon-carbon double bond |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103626895B (en) | 2016-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2670752C9 (en) | Olefin based polymer with excellent processing ability | |
| Beckerle et al. | Living isospecific styrene polymerization by chiral benzyl titanium complexes that contain a tetradentate [OSSO]-type bis (phenolato) ligand | |
| CN104558282A (en) | Catalyst component used for olefin polymerization and preparation method thereof as well as catalyst used for olefin polymerization and application | |
| CN101880342B (en) | Olefin polymerization catalyst and preparation and application thereof | |
| TWI644896B (en) | Catalyst component, catalyst and application for olefin polymerization | |
| CN102603932B (en) | Solid catalyst component and catalyst for olefinic polymerization | |
| CN102558404A (en) | Polyol ether polyolefin catalyst and preparation and application thereof | |
| CN104761664A (en) | Catalyst composition used in olefin polymerization and application thereof | |
| CN103626895B (en) | For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction | |
| CN104053682A (en) | High activity catalyst component for olefin polymerization and method of using the same | |
| CN102453148B (en) | Olefin polymerization catalyst component, olefin polymerization catalyst and olefin polymerization method | |
| CN103626896B (en) | For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction | |
| CN104558292A (en) | Preparation method of catalyst for olefin polymerization | |
| CN102453133A (en) | Olefin polymeric catalyst system and olefin polymerization method by using catalyst system thereof | |
| CN109096424A (en) | A kind of catalyst and olefine polymerizing process for olefinic polymerization | |
| CN101970507A (en) | Catalyst for the polymerization of olefins | |
| CN102276763A (en) | Preparation method of ethylene polymerization catalyst with slurry process | |
| CN103626893B (en) | For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction | |
| CN101885793A (en) | Ethylene polymerization catalyst, preparation and application thereof | |
| CN105315390A (en) | Catalyst composition for olefin polymerization and application thereof | |
| CN109694420A (en) | Catalyst system and pre-polymerized catalyst and olefine polymerizing process for olefinic polymerization | |
| CN104513327A (en) | Olefin polymerization catalyst composition and applications thereof | |
| CN103626894B (en) | For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction | |
| JP5892032B2 (en) | Method for producing catalyst component for α-olefin polymerization, method for producing catalyst for α-olefin polymerization, and method for producing α-olefin polymer | |
| JP2019172944A (en) | METHOD FOR PRODUCING PROPYLENE/α-OLEFIN COPOLYMER |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |