CN103626895B - 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
- Publication number
- CN103626895B CN103626895B CN201210303463.6A CN201210303463A CN103626895B CN 103626895 B CN103626895 B CN 103626895B CN 201210303463 A CN201210303463 A CN 201210303463A CN 103626895 B CN103626895 B CN 103626895B
- Authority
- CN
- China
- Prior art keywords
- compound
- alkyl
- ethyl
- methyl
- 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.)
- Active
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a kind of catalyst component for olefinic polyreaction and catalyzer thereof, described catalyst component is prepared by the method for following step: magnesium compound mixes with organic alcohol compound and inert solvent by (1), adds precipitation additive reaction; (2) alcohol adduct that step (1) obtains is contacted with under compound titanium solution low temperature, then add electron donor compound a and b reacts, filter to isolate solid particulate; (3) solid particulate is joined in compound titanium solution, stir and react, filtering to isolate solid particulate; 4) wash solid particulate with inert solvent, after drying, obtain catalyst component.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-kind of olefin polymerization catalyst components and prepare the method for described catalyzer, be more particularly to-kind by two kinds of composite olefin polymerization catalyst components and application thereof 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 atom, wherein electron donor compound be in catalyst component requisite one-tenth divide it-, and constantly to update 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, 2,2-diisobutyl-1,3-Propanal dimethyl acetals and 9,1, the 3-diether compounds such as 9-bis-(methoxymethyl) fluorenes are as electron donor.But, the above-mentioned disclosed catalyzer defect that ubiquity molecular weight distribution is narrow in the practical application of olefinic polymerization prepared using diether compound as internal electron donor, disclosed in Chinese patent CN102040485A and CN102040684A 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 that the hydrogen response of two ethers catalyzer is good, 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 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 solution;
(2) solution that step (1) obtains is contacted with under titanium compound low temperature, under precipitation additive exists, separate out solids; In precipitation solids process or after separating out solids, add electron donor compound a and b reacts, 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
1-kind of C
2~ C
7the alkyl of straight or branched, or H is wherein optionally by-individual 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, 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; R
2be 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.
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 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-.
(3) by after solid particulate and compound titanium solution contact reacts, after filtration, washing, drying, catalyst component is obtained.
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, R
2it is the compound of phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, Cvclopropvlmethvl 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 be selected from wherein-individual halogen atom in magnesium dihalide, the hydrate of magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula by-oxyl or halo-oxyl in the derivative of replacing-kind, or their mixture, preferred magnesium dihalide, such as magnesium dichloride, dibrominated magnesium, diiodinating magnesium; 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, one in naphthenic hydrocarbon or aromatic hydrocarbons 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 is the alkyl of 1 ~ 20, X
ifor halogen, n=1 ~ 4; Described precipitation additive is the one in organic acid anhydride, organic acid, ether, ketone, alcohol ester, or their mixture.
In above-mentioned catalyst component, preferably magnesium compound and organic alcohol compound are mixed to form solution by 2 ~ 5 mol ratios and inert solvent in described step (1), be warming up to 120 ~ 150 DEG C, add precipitation additive by magnesium/precipitation additive mol ratio 5 ~ 10, react 1 ~ 5 hour.
In above-mentioned catalyst component, according to titanium/magnesium mol ratio 20 ~ 50, the alcohol adduct solution of magnesium is contacted under the cold condition of-15 ~-40 DEG C with compound titanium solution in described step (2), be warming up to 90 ~ 110 DEG C, in precipitation solids process or after separating out solids, add electron donor compound a and b reacts, 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 ensure that final resulting polymers can have higher degree of isotacticity, preferred electron donor compound a is 0.02 ~ 0.1 mole, 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.
In above-mentioned catalyst component preparation method, preferably according to titanium/magnesium mol ratio 20 ~ 50, solid particulate is joined in compound titanium solution in described step (3), stir and 100 ~ 130 DEG C of reactions 1.5 ~ 3 hours, filter to isolate solid particulate.
Present invention also offers a kind of catalyzer for olefinic polymerization, comprise the reaction product of following component:
A. the catalyst component of the present invention prepared of aforesaid method;
B. organo-aluminium compound;
C. optional Component silicoorganic compound.
Wherein A (with Ti content meter): B:C=1 mole: 20 ~ 800 moles: 0 ~ 100 mole
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 halide 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 preferred triethyl aluminum, triisobutyl aluminium.
In above-mentioned catalyzer, in order to obtain the olefin polymer of very high taxis, external donor compound need be added, 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 also can be halogen or hydrogen atom.Concrete example comprises: trimethylmethoxysilane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, cyclohexyl methyl diethoxy silane, Cyclohexylmethyldimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, the silicoorganic compound such as vinyltrimethoxy silane, can preferably Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane.
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.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 polymerization process in reactor, or catalyzer can carry out prepolymerization before adding the-individual 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, adopt propylene or other and propylene molar 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 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 as in continuous polymerization technique-part carries out online, or to 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 the requirement of suitability for industrialized 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.
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 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 5mmol; 9,9 one two (methyl methoxy base) fluorenes 5mmol, 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.
(2) propylene polymerization
Volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, add AlEt32.5mmol, Cyclohexylmethyldimethoxysilane (CHMMS) 0.lmmol, 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 2
With embodiment 1, difference is to be warming up to 100 DEG C, " 2-n-pentyl-2-(2-ethylhexyl will be added)-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 DEG C, " 2-n-pentyl-2-(2-ethylhexyl will be added)-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 first to be warming up to 80 DEG C, add compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 5mmol, then be warming up to 100 DEG C, add compound 9,9 one two (methyl methoxy base) fluorenes 5mmol, concrete outcome is in table 1.
Embodiment 5
With embodiment 1, add 9.0NL hydrogen when difference is polymerization, concrete outcome is in table 2.Embodiment 6
With embodiment 2, 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 100 DEG C, " 2-n-pentyl-2-(2-ethylhexyl will be added)-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 DEG C, " 2-n-pentyl-2-(2-ethylhexyl will be added)-1; 3-Propanal dimethyl acetal 5mmol; 9; 9 one two (methyl methoxy base) fluorenes 5mmol " replace with " adding compound 9,9 one two (methyl methoxy base) fluorenes 6mmol ", concrete outcome is in table 1.
Comparative example 3
With comparative example 1, 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 is obviously wide than simple b class internal electron donor (comparative example 2) that uses, and degree of isotacticity also uses increasing of a class electron donor (comparative example 1) than simple, the more important thing is, improve polymerization time hydrogen concentration time, as can be seen from the data of table 2 we, a class internal electron donor (comparative example 3) is used if simple, under high hydrogen concentration, the degree of isotacticity of resulting polymers sharply declines, 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 (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 solution;
(2) solution that step (1) obtains is contacted with under titanium compound low temperature, under precipitation additive exists, separate out solids; In precipitation solids process or after separating out solids, add electron donor compound a and b reacts, 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
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;
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 filtration, washing, drying, catalyst component is obtained.
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, and 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 add at differential responses temperature.
5. the catalyst component for olefinic polyreaction according to claim 1, in the diether compounds of step (2) described general formula (I), R is methyl or ethyl.
6. the catalyst component for olefinic polyreaction according to claim 1, in the diether compounds of step (2) described general formula (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 step (2) described general formula (I), R
2phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, Cvclopropvlmethvl 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, Cvclopropvlmethvl 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
2~ C
7the alkyl of straight or branched and R
2phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, Cvclopropvlmethvl 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 magnesium dihalide, in the hydrate of magnesium dihalide or alcohol adduct or magnesium dihalide molecular formula one of them halogen atom by-oxyl or halo-oxyl the one in the derivative of replacing; Described organic alcohol compound is C
2~ C
8monohydroxy-alcohol; Described inert solvent is C
1~ C
20alkane, one in naphthenic hydrocarbon or aromatic hydrocarbons 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 is the alkyl of 1 ~ 20, X
ifor halogen, n=1 ~ 4; Described precipitation additive is the one 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 used for CH
2the catalyzer of=CHR olefinic polyreaction, wherein R is hydrogen or C
1~ C
6alkyl or aryl, comprise the reaction product of 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 CN103626895A (en) | 2014-03-12 |
| CN103626895B true 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) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107840909B (en) * | 2016-09-21 | 2021-04-13 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization, catalyst system and prepolymerization catalyst |
| CN113136239B (en) * | 2020-01-19 | 2022-05-13 | 清华大学 | Utilization method of ethylene cracking tar and application of compound containing carbon-carbon double bond |
Family Cites Families (6)
| 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 |
| JPS588686B2 (en) * | 1978-12-01 | 1983-02-17 | チッソ株式会社 | Method for producing α↓-olefin polymer |
| IT1245249B (en) * | 1991-03-27 | 1994-09-13 | Himont Inc | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| IL117114A (en) * | 1995-02-21 | 2000-02-17 | Montell North America Inc | Components and catalysts for the polymerization ofolefins |
| CN1137155C (en) * | 1999-12-06 | 2004-02-04 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| CN1169845C (en) * | 2002-02-07 | 2004-10-06 | 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
Also Published As
| Publication number | Publication date |
|---|---|
| CN103626895A (en) | 2014-03-12 |
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 | |
| CN103492397A (en) | Pyridyldiamido transition metal complexes, production and use thereof | |
| CN101735346A (en) | Catalyst for propylene homopolymerization and copolymerization, and preparation method and application thereof | |
| CN101880342B (en) | Olefin polymerization catalyst, preparation and application thereof | |
| Wang et al. | [ONNO]-type oxovanadium (V) complexes containing amine pyridine bis (phenolate) ligands: synthesis, characterization and catalytic behavior for ethylene (co) polymerization | |
| TWI644896B (en) | Catalyst component, catalyst and application for olefin polymerization | |
| CN103626895B (en) | For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction | |
| Chen et al. | Novel nickel (II) and copper (II) complexes with phenoxy-imidazole ligands: Syntheses, crystal structures and norbornene addition polymerization | |
| CN104053682A (en) | High activity catalyst component for olefin polymerization and method of using the same | |
| CN103626896B (en) | For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction | |
| CN101759816B (en) | Method for preparing a catalyst component for olefinic polymerization, and a catalyst component thereof | |
| CN104558292A (en) | Preparation method of catalyst for olefin polymerization | |
| CN103626894B (en) | For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction | |
| CN105085732A (en) | Catalyst component for olefin polymerization, and catalyst thereof | |
| CN102453133A (en) | Olefin polymeric catalyst system and olefin polymerization method by using catalyst system thereof | |
| CN101906180B (en) | Olefin polymerization catalyst and preparation method thereof | |
| CN101885795B (en) | Electron donor catalyst, preparation and application | |
| CN101885793B (en) | Ethylene polymerization catalyst, preparation and application thereof | |
| CN101970507A (en) | Catalyst for olefin polymerization | |
| CN101472961A (en) | Catalyst components for the polymerization of olefins based on 1, 3-diethers | |
| CN103626893B (en) | For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction | |
| CN109694420A (en) | Catalyst system and pre-polymerized catalyst and olefine polymerizing process for olefinic polymerization | |
| CN100513432C (en) | Catalyst component for olefinic polymerization and its catalyst |
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 |