CN101423572A - Catalyst component for olefin polymerization and catalyst thereof - Google Patents
Catalyst component for olefin polymerization and catalyst thereof Download PDFInfo
- Publication number
- CN101423572A CN101423572A CNA2007101766713A CN200710176671A CN101423572A CN 101423572 A CN101423572 A CN 101423572A CN A2007101766713 A CNA2007101766713 A CN A2007101766713A CN 200710176671 A CN200710176671 A CN 200710176671A CN 101423572 A CN101423572 A CN 101423572A
- Authority
- CN
- China
- Prior art keywords
- indolizine
- catalyst component
- dioctyl phthalate
- titanium
- alkyl
- 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 relates to an olefinic-polymerized catalytic composition, which adopts at least one purrocoline diester compound in a general formula (I) as an internal electron donor. The catalytic composition is used for olefin, and can obtain a polymer with quite high stereospecificity particularly when propylene is copolymerized. The invention also discloses a catalyst containing the catalytic composition.
Description
Technical field
The present invention relates to be used for catalyst component in olefin polymerisation and catalyzer thereof, particularly a kind of catalyst component and catalyzer thereof that is used for propylene polymerization.
Background technology
As everyone knows, with magnesium, titanium, halogen and electron donor solid titanium catalyst component, can be used for CH as basal component
2=CHR olefinic polyreaction particularly can obtain the polymkeric substance of higher yields and higher tacticity in the alpha-olefine polymerizing with 3 carbon or more carbon atoms.Wherein, electron donor is one of requisite composition in the catalyst component, and along with the development of electron donor compound has caused polyolefin catalyst constantly to update.
Previously, reported multiple electron donor compound in the document in a large number, for example polycarboxylic acid, monobasic or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and derivative thereof, wherein comparatively commonly used is binary aromatic carboxylic acid's ester class, as n-butyl phthalate or diisobutyl phthalate (CN85100997A) etc.
In recent years, people attempt adopting other compounds as the electron donor in the olefin polymerization catalyst components, US4971937, US2004014597 and EP728769 have adopted special 1, the 3-diether compound is as electron donor, as 2, and 2-diisobutyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal and 9,9-two (methoxymethyl) fluorenes etc. also can be referring to CN1042547A, CN1143651A, US2003027715 and WO03076480.The disclosed catalyst component that is used for olefinic polyreaction of CN1054139A, it is special 1 to adopt, and the 3-cyclohexadione compounds is as electron donor, as 2,2,6,6-tetramethyl--3,5-heptadione and 2,2,4,6,6-pentamethyl--3,5-heptadione etc.
Special dibasic aliphatic carboxylic acid esters and the diol-lipid compound of one class disclosed again recently, as (referring to CN1313869A, CN1236373A, CN1236374A, CN1552741A, CN1213080C, CN1542024A, CN1552742A and CN1552740A) such as succinate, malonic ester, glutarate, glycol ester, propylene glycol ester, butanediol ester, pentadiol ester and hexylene glycol esters.CN1313869A, US6818583 and WO2004024785 disclose the succinate that replaces is given body as the internal electron of the catalyst component that is used for olefinic polymerization application.The use of these electron donor compounds not only can improve activity of such catalysts, and the polyacrylic molecular weight distribution of gained is obviously widened.But when not adopting the external electron donor component, the degree of isotacticity of resulting polymers is still lower.
Summary of the invention
The object of the present invention is to provide a kind of CH of being used for
2The catalyst component of=CHR olefinic polyreaction, wherein R is hydrogen or the hydrocarbyl group with 1-12 carbon atom.Another object of the present invention provides the catalyzer that contains above-mentioned catalyst component.
Catalyst component of the present invention by weight percentage, comprises 10-25% magnesium, 1-10% titanium, 40-60% halogen and 1-30% internal electron donor, and described internal electron donor is selected from least a indolizine diester compound in the general formula (I):
Wherein, radicals R
1And R
2Being same to each other or different to each other, is C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching; Radicals R
3Be hydrogen or C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching.
In above-mentioned indolizine diester general formula compound, R
1And R
3Be preferably C
1-C
10Alkyl, cycloalkyl or arylalkyl, preferred especially C
1-C
10Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or neo-pentyl, further preferred ethyl, sec.-propyl, normal-butyl or isobutyl-.R
3Be preferably alkyl, aryl or arylalkyl.
The example of suitable above-mentioned general formula compound includes but not limited to:
3-ethanoyl indolizine-1; 2-dioctyl phthalate dimethyl ester; 3-ethanoyl indolizine-1; the 2-dicarboxylate; 3-ethanoyl indolizine-1; 2-dioctyl phthalate di-n-propyl ester; 3-ethanoyl indolizine-1; 2-dioctyl phthalate diisopropyl ester; 3-ethanoyl indolizine-1; 2-dioctyl phthalate di-n-butyl; 3-ethanoyl indolizine-1; 2-dioctyl phthalate diisobutyl ester; 3-ethanoyl indolizine-1; 2-dioctyl phthalate two peopentyl esters; 3-benzoyl indolizine-1; 2-dioctyl phthalate dimethyl ester; 3-benzoyl indolizine-1; the 2-dicarboxylate; 3-benzoyl indolizine-1; 2-dioctyl phthalate di-n-propyl ester; 3-benzoyl indolizine-1; 2-dioctyl phthalate diisopropyl ester; 3-benzoyl indolizine-1; 2-dioctyl phthalate di-n-butyl; 3-benzoyl indolizine-1; 2-dioctyl phthalate diisobutyl ester; 3-benzoyl indolizine-1; 2-dioctyl phthalate two peopentyl esters; 3-phenylacetyl indolizine-1; 2-dioctyl phthalate dimethyl ester; 3-phenylacetyl indolizine-1; the 2-dicarboxylate; 3-phenylacetyl indolizine-1; 2-dioctyl phthalate di-n-propyl ester; 3-phenylacetyl indolizine-1; 2-dioctyl phthalate diisopropyl ester; 3-phenylacetyl indolizine-1; 2-dioctyl phthalate di-n-butyl; 3-phenylacetyl indolizine-1; 2-dioctyl phthalate diisobutyl ester or 3-phenylacetyl indolizine-1 ,-dioctyl phthalate two peopentyl esters.
The synthetic method of indolizine diester compound of the present invention can be referring to document: Landberg B.E.; Lown J.W.J.C.S.Perkin I 1975,1326.; Sarkunam K.; Nallu M.J.Heterocyclic Chem.2005,42,5..
Magnesium in the catalyst component can be by size-grade distribution 20～250 μ m, and general formula is Mg (OR ') mX
(2-m)The magnesium halide alcohol adduct of pROH provides, and R ' is C in the formula
1～C
20Alkyl, arylalkyl or aryl; X is a halogen; M is the integer of 0 ≦ m＜2; N is the decimal or the integer of 0＜p＜6; R is C
1-C
20The alkyl or aryl alkyl.
Magnesium halide in the magnesium halide alcohol adduct is selected from a kind of in magnesium dichloride, dibrominated magnesium, chloro magnesium methylate or the chloro magnesium ethylate, preferred magnesium dichloride; Alcohol in the magnesium halide alcohol adduct is selected from a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the isopropylcarbinol, preferred alcohol.
After magnesium halide alcohol adduct adopts magnesium halide and alcohol to be total to heat of solution, high pressure ejection or high-speed stirring, the method that is solidified into microsphere particle in heat-eliminating medium obtains, and concrete grammar is referring to the associated description among the US4399054.
Titanium in the catalyst component can be TiX by general formula
n(OR)
4-nCompound provide, R is that carbonatoms is the alkyl of 1-20 in the formula; X is a halogen; N=1-4.Concrete compound is as titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium or trichlorine one ethanolato-titanium, preferred titanium tetrachloride.
The preparation method of catalyst component of the present invention comprises: (1) joins spherical magnesium halide alcohol adduct in-40～10 ℃ the titanium compound, reacts 1～4 hour, and the mol ratio of magnesium and titanium is 1:5～1:50; (2) be warming up to 30～80 ℃, add the internal electron donor compound, the mol ratio of magnesium and internal electron donor compound is 2:1～15:1; (3) be warming up to 100～150 ℃ again, reacted 1～4 hour; (4) add titanium compound with step (1) same amount after filtering again, in 110～130 ℃ of reactions 1～4 hour, more after filtration, washing obtained after the drying.
With above-mentioned catalyst component is main ingredient, and the present invention also can further be provided for the catalyzer of olefinic polymerization.Catalyzer specifically comprises:
(a) contain magnesium, titanium, halogen and be selected from the catalyst component of at least a indolizine diester compound in the general formula (I);
(b) alkylaluminium cpd;
(c) randomly, external electron donor.
Wherein, alkylaluminium cpd (b) is selected from trialkyl aluminium compound, as the mixture of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum or tri-n-octylaluminium, trialkylaluminium and aluminum alkyl halide or alkyl aluminum hydride, or alkylaluminoxane.
The external electron donor component can add as required selectively.Obtain the olefin polymer of taxis very high (as isotactic index greater than 99%) for needs, suggestion adds the external electron donor compound.
It is R that external electron donor can be selected general formula
nSi (OR ')
4-nSilicoorganic compound, the integer of 0≤n in the formula≤3; R is of the same race or different alkyl, cycloalkyl or aryl with R ', the optional heteroatoms that contains; R also can be halogen or hydrogen atom.Concrete silicoorganic compound are as the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl-t-butyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane, preferred cyclohexyl methyl dimethoxy silane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane.
1 of the also optional self-drifting of external electron donor (II), 3-two ethers:
R wherein
I, R
II, R
III, R
IV, R
VAnd R
VICan be identical or different, can be hydrogen or have the hydrocarbyl group of 1 to 18 carbon atom; R
VIIAnd R
IIICan be identical or different, can be hydrocarbyl group with 1 to 18 carbon atom; R
I-R
VIIIGroup in one or morely can also link up into ring.Preferably, R
VIIAnd R
VIIIBe selected from C
1-C
4Alkyl group, R
IIIAnd R
IVForm undersaturated condensed ring and R
I, R
II, R
VAnd R
VIBe hydrogen.Especially preferably use 9, two (methoxymethyl) fluorenes of 9-.
With titanium: aluminium: the molar ratio computing between the external electron donor compound (c), the amount ratio in the catalyzer between each component are 1:5-1000:0-500; Be preferably 1:25-100:25-300.
Catalyzer of the present invention is used for olefinic polymerization, can access the polymkeric substance of very high isotactic index when the equal polymerization of special propylene or the copolymerization of propylene and other alkene.Simultaneously, do not get rid of the copolymerization that is applicable to production polyethylene and ethene and alpha-olefin such as propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene or 1-octene yet.
Can adopt the whole bag of tricks of the prior art when being used for propylene polymerization, can in liquid phase or gas phase, carry out, also can under the combination operation of liquid and gas polymerization stage, carry out.Polymerization is carried out at 0～150 ℃ usually, preferred 40～90 ℃.Polymerization pressure is 0.01～10MPa.The hydrogen of chain-transfer agent effect or other compounds can be played and the molecular weight of controlling polymers can be used for.
The present invention is by adopting novel internal electron donor indolizine diester compound, can obtain the catalyzer of high comprehensive performance, when being used for propylene (being total to) polymerization, can obtain gratifying polymerization yield rate, and the stereospecificity of polymkeric substance is very high, even when not using external electron donor, still can obtain high normal polymkeric substance, catalyzer is also fine to the susceptibility of hydrogen accent simultaneously, and the molecular weight distribution broad of resulting polymers helps the exploitation of the different trades mark of polymkeric substance.
Embodiment
Embodiment given below is for the present invention is described better, rather than limits the invention.
Testing method:
1, polymericular weight and molecular weight distribution MWD (MWD=M
w/ M
n): adopting the gel permeation chromatography method, is that solvent is measured down at 135 ℃ with the orthodichlorobenzene with Alliance-GPCV2000.
2, polymkeric substance degree of isotacticity: adopt the heptane extraction process to measure (heptane boiling extracting 8 hours), promptly 1 restrain the exsiccant polymer samples, be placed in the extractor with the extracting of boiling heptane after 8 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 1 ratio.
3, the mensuration of melt index: measure according to μ PXRZ-400C.
4, the mensuration of titanium percentage composition: according to spectrophotometry.
5, the mensuration of internal electron donor percentage composition: according to the Autosystem XL of PE company gas chromatograph for determination.
One, the indolizine diester compound is synthetic
Only with 3-benzoyl indolizine-1, the 2-dimethyl dicarboxylate synthesizes example, and concrete grammar is as follows:
(1) pyridinium salt of Synthetic 2-bromoacetophenone
Add 8g pyridine and 150ml ethyl acetate in the 250ml reaction flask, add the 19.9g bromoacetophenone under stirring, stirred 8 hours under the room temperature, have a large amount of white precipitates to generate, suction filtration with the ethyl acetate washing, is weighed after the drying, gets 27.4 gram white powders, yield 98%.
(2) synthetic 3-benzoyl indolizine-1, the 2-dimethyl dicarboxylate
Add the homemade pyridinium salt of 25g, 22g Anhydrous potassium carbonate and 100mlDMF in the 250ml flask, stirring drips 11.4g dimethyl butyn (DMAD) after half an hour under the room temperature, adds the back and continues to stir 8 hours under the room temperature.Add in the dilute hydrochloric acid and the back ethyl acetate extraction, salt washing 2 times is washed 1 time, uses anhydrous sodium sulfate drying, filter, and solvent evaporated, column chromatography for separation gets yellow solid 19.7g, yield 74%.
1H NMR (TMS, CDCl
3, 400MHz) analytical results: δ 7.08-9.62 (m, 9H, aromatic hydrocarbons H); δ 3.88 (s, 3H, CH
3); δ 3.32 (s, 3H, CH
3).
Two, the preparation of catalyst component
Embodiment 1-12
Under the anhydrous and oxygen-free condition, in 500 milliliter of four neck round-bottomed flask of a process abundant metathetical of high pure nitrogen, add TiCl
4100ml and toluene 60ml are cooled to-20 ℃, add 10.0gMgCl
22.8CH
3CH
2OH ball type carrier (according to the method preparation of USP4399054).Rise to 0 ℃ in 1 hour, continuing to heat up rose to 20 ℃ in 2 hours, and continuing to heat up rose to 40 ℃ in 1 hour, added corresponding indolizine diester compound (self-control) 7.4mmol in the table 1 respectively, was warming up to 100 ℃ in 1 hour, kept venting filtrate 2 hours.Add TiCl
4100ml rose to 120 ℃ in 1 hour, kept venting filtrate 2 hours.Add anhydrous hexane 60ml, boiling attitude washing 5 times adds anhydrous hexane 60ml then, and normal temperature washing 3 times is at last with the solid catalytic component vacuum-drying that obtains.
Comparative example 1-4
Prepare catalyst component by the foregoing description, just internal electron donor is replaced with n-butyl phthalate, dibutyl succinate, 2 respectively, 3-di-isopropyl ethyl succinate and 2,4-pentanediol dibenzoate.
Three, propylene polymerization experiment
The catalyst component of the foregoing description 1-12 and comparative example 1-4 is carried out propylene polymerization respectively.Usually step is: volume is the stainless steel autoclave of 5L, after high pure nitrogen is fully replaced, adds AlEt
32.5mmol external electron donor methylcyclohexyl dimethoxy silane (CHMMS) 0.1mmol adds catalyst component 10mg and the 1.2L hydrogen of the foregoing description 1-24 again, feeds liquid propene 2.3L, is warming up to 70 ℃, keeps this temperature 1 hour.Cooling, pressure release to 1 normal atmosphere obtains the PP powder.Polymerization result is listed in table 1.
Table 1. propylene polymerization result
Four, the propylene polymerization result of different external electron donors relatively
Catalyst component is with embodiment 8, and polymerization process is with aforementioned, and just external electron donor changes down the external electron donor described in the tabulation into.
The polymerization result of the different external electron donors of table 2. relatively
| External electron donor | Polymerization activity kgPP/gcat | Degree of isotacticity (%) | Molecular weight distribution | Melting index g/10min |
| Methylcyclohexyl dimethoxy silane | 57 | 99.0 | 8.5 | 0.9 |
| Dicyclopentyl dimethoxyl silane | 52 | 98.3 | 8.3 | 1.0 |
| Diisopropyl dimethoxy silane | 49 | 97.8 | 8.0 | 1.2 |
| Di-n-butyl dimethoxy silane | 47 | 98.1 | 7.8 | 1.0 |
| Second, isobutyl dimethoxy silane | 41 | 98.5 | 7.8 | 1.0 |
| 9, two (methoxymethyl) fluorenes of 9- | 51 | 99.2 | 7.0 | 0.9 |
Five, vinyl polymerization experiment
Volume is the stainless steel autoclave of 4L, after the abundant pump drainage displacement of high pure nitrogen, starts stirring, progressively adds the catalyst component and the 2.5mmol promotor AlEt of 1L hexane, 10mg embodiment 8 gained under nitrogen protection in still
3After being warming up to 75 ℃, in still, replenish an amount of high-purity hydrogen, make that hydrogen partial pressure is 0.3Mpa in the still, after 5 minutes in still make-up ethylene gas make its dividing potential drop reach 0.75MPa, the dividing potential drop of keeping ethylene gas is constant, make system temperature keep 80 ℃, after 3 hours, cooling discharge, polymkeric substance except that desolvating, is obtained polyethylene 277g after the thorough drying.
Six, ethene and copolymerization of propylene experimental result
Volume is the stainless steel autoclave of 4L, after the abundant pump drainage displacement of high pure nitrogen, starts stirring, progressively adds the catalyst component and the 2.5mmol promotor AlEt of 1L hexane, 10mg embodiment 8 gained under nitrogen protection in still
3Feed liquid propene 2.3L, be warming up to 75 ℃ after, in still, replenish an amount of high-purity hydrogen, making the interior hydrogen partial pressure of still is 0.3MPa, make-up ethylene gas makes its dividing potential drop reach 0.75MPa in still then, and the dividing potential drop of keeping ethylene gas is constant, makes system temperature keep 80 ℃, after 3 hours, cooling discharge except that desolvating, obtains polymer powders 469g with polymkeric substance after the thorough drying.
Claims (22)
1. be used for catalyst component in olefin polymerisation, by weight percentage, comprise 10%-25% magnesium, 1%-10% titanium, 40%-60% halogen and 1%-30% internal electron donor, it is characterized in that described internal electron donor is selected from least a indolizine diester compound in the general formula (I):
Wherein, radicals R
1And R
2Being same to each other or different to each other, is C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching; Radicals R
3Be hydrogen or C
1-C
20Line style or alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or the kiki fang alkyl group of branching.
2. catalyst component according to claim 1 is characterized in that in the indolizine diester general formula compound R
1And R
2Be C
1-C
10Alkyl, cycloalkyl or arylalkyl.
3. catalyst component according to claim 2 is characterized in that in the indolizine diester general formula compound R
1And R
2Be C
1-C
10Alkyl.
4. catalyst component according to claim 3 is characterized in that in the indolizine diester general formula compound R
1And R
2Be ethyl, sec.-propyl, normal-butyl or isobutyl-.
5. catalyst component according to claim 1 is characterized in that in the indolizine diester general formula compound R
3Be alkyl, aryl or arylalkyl.
6. catalyst component according to claim 1; it is characterized in that indolizine diester general formula compound is a 3-ethanoyl indolizine-1; 2-dioctyl phthalate dimethyl ester; 3-ethanoyl indolizine-1; the 2-dicarboxylate; 3-ethanoyl indolizine-1; 2-dioctyl phthalate di-n-propyl ester; 3-ethanoyl indolizine-1; 2-dioctyl phthalate diisopropyl ester; 3-ethanoyl indolizine-1; 2-dioctyl phthalate di-n-butyl; 3-ethanoyl indolizine-1; 2-dioctyl phthalate diisobutyl ester; 3-ethanoyl indolizine-1; 2-dioctyl phthalate two peopentyl esters; 3-benzoyl indolizine-1; 2-dioctyl phthalate dimethyl ester; 3-benzoyl indolizine-1; the 2-dicarboxylate; 3-benzoyl indolizine-1; 2-dioctyl phthalate di-n-propyl ester; 3-benzoyl indolizine-1; 2-dioctyl phthalate diisopropyl ester; 3-benzoyl indolizine-1; 2-dioctyl phthalate di-n-butyl; 3-benzoyl indolizine-1; 2-dioctyl phthalate diisobutyl ester; 3-benzoyl indolizine-1; 2-dioctyl phthalate two peopentyl esters; 3-phenylacetyl indolizine-1; 2-dioctyl phthalate dimethyl ester; 3-phenylacetyl indolizine-1; the 2-dicarboxylate; 3-phenylacetyl indolizine-1; 2-dioctyl phthalate di-n-propyl ester; 3-phenylacetyl indolizine-1; 2-dioctyl phthalate diisopropyl ester; 3-phenylacetyl indolizine-1; 2-dioctyl phthalate di-n-butyl; 3-phenylacetyl indolizine-1; 2-dioctyl phthalate diisobutyl ester or 3-phenylacetyl indolizine-1,2-dioctyl phthalate two peopentyl esters.
7. catalyst component according to claim 1 is characterized in that magnesium in the catalyst component by size-grade distribution 20～250 μ m, and general formula is Mg (OR ') mX
(2-m)The magnesium halide alcohol adduct of pROH provides, and R ' is C in the formula
1～C
20Alkyl, arylalkyl or aryl; X is a halogen; M is the integer of 0 ≦ m＜2; N is the decimal or the integer of 0＜p＜6; R is C
1-C
20The alkyl or aryl alkyl.
8. catalyst component according to claim 7 is characterized in that providing in the magnesium halide alcohol adduct of magnesium, and magnesium halide is a kind of in magnesium dichloride, dibrominated magnesium, chloro magnesium methylate or the chloro magnesium ethylate; Alcohol in the magnesium halide alcohol adduct is a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the isopropylcarbinol.
9. catalyst component according to claim 8, it is characterized in that providing the magnesium halide in the magnesium halide alcohol adduct of magnesium is magnesium dichloride; Alcohol in the magnesium halide alcohol adduct is ethanol.
10. catalyst component according to claim 1 is characterized in that the titanium in the catalyst component is TiX by general formula
n(OR)
4-nCompound provide, R is that carbonatoms is the alkyl of 1-20 in the formula; X is a halogen; N=1-4.
11. catalyst component according to claim 10 is characterized in that the titanium in the catalyst component is provided by titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium or trichlorine one ethanolato-titanium.
12. catalyst component according to claim 11 is characterized in that the titanium in the catalyst component is provided by titanium tetrachloride.
13. a catalyzer that comprises one of the described catalyst component of claim 1 to 12 is characterized in that catalyzer comprises:
A) one of the described catalyst component of claim 1 to 12;
B) alkylaluminium cpd;
C) randomly, external electron donor.
14. catalyzer according to claim 13 is characterized in that alkylaluminium cpd is a trialkyl aluminium compound.
15. catalyzer according to claim 14, it is characterized in that alkylaluminium cpd is the mixture of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium, trialkylaluminium and aluminum alkyl halide or alkyl aluminum hydride, or alkylaluminoxane.
16. catalyzer according to claim 13 is characterized in that external electron donor is that general formula is R
nSi (OR ')
4-nSilicoorganic compound, the integer of 0≤n in the formula≤3; R is of the same race or different alkyl, cycloalkyl or aryl with R '.
17. catalyzer according to claim 16, it is characterized in that external electron donor is the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl-t-butyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane, preferred cyclohexyl methyl dimethoxy silane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane.
18. catalyzer according to claim 13 is characterized in that external electron donor is 1 of a general formula (II), 3-two ethers:
R wherein
I, R
II, R
III, R
IV, R
VAnd R
VICan be identical or different, for hydrogen or have the hydrocarbyl group of 1 to 18 carbon atom; R
VIIAnd R
IIICan be identical or different, for having the hydrocarbyl group of 1 to 18 carbon atom; R
1-R
VIIIGroup in one or morely can link up into ring.
19. catalyzer according to claim 18 is characterized in that in the external electron donor general formula R
VIIAnd R
VIIIBe C
1-C
4Alkyl group; R
IIIAnd R
IVForm undersaturated condensed ring; R
I, R
II, R
VAnd R
VIBe hydrogen.
20. catalyzer according to claim 19 is characterized in that external electron donor is 9, two (methoxymethyl) fluorenes of 9-.
21. catalyzer according to claim 13 is characterized in that with titanium: aluminium: the molar ratio computing of external electron donor compound, the consumption between each component are 1:5-1000:0-500.
22. catalyzer according to claim 21 is characterized in that with titanium: aluminium: the molar ratio computing of external electron donor compound, the consumption between each component are 1:25-100:25-300.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101766713A CN101423572B (en) | 2007-11-01 | 2007-11-01 | Catalyst component for olefin polymerization and catalyst thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101766713A CN101423572B (en) | 2007-11-01 | 2007-11-01 | Catalyst component for olefin polymerization and catalyst thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101423572A true CN101423572A (en) | 2009-05-06 |
| CN101423572B CN101423572B (en) | 2011-09-07 |
Family
ID=40614473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101766713A Active CN101423572B (en) | 2007-11-01 | 2007-11-01 | Catalyst component for olefin polymerization and catalyst thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101423572B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276601A (en) * | 2011-06-07 | 2011-12-14 | 浙江大学 | Preparation method of indolizine derivative |
| CN104403028A (en) * | 2014-11-19 | 2015-03-11 | 中国科学院化学研究所 | Polypropylene catalyst containing carbonic ester external electron donor |
| CN106045994A (en) * | 2016-06-12 | 2016-10-26 | 上海大学 | Perfluoroalkyl indolizine derivative and synthesis method thereof |
| US11530281B2 (en) | 2016-08-19 | 2022-12-20 | Institute Of Chemistry, Chinese Academy Of Sciences | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6818583B1 (en) * | 1999-04-15 | 2004-11-16 | Basell Poliolefine Italia S.P.A. | Components and catalysts for the polymerization of olefins |
| CN1310963C (en) * | 2003-05-30 | 2007-04-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization reaction and catalyst |
| CN1282670C (en) * | 2004-04-30 | 2006-11-01 | 中国石油化工股份有限公司 | Catalyst components for olefinic polyreaction and catalyst thereof |
-
2007
- 2007-11-01 CN CN2007101766713A patent/CN101423572B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276601A (en) * | 2011-06-07 | 2011-12-14 | 浙江大学 | Preparation method of indolizine derivative |
| CN102276601B (en) * | 2011-06-07 | 2012-10-17 | 浙江大学 | Preparation method of indolizine derivative |
| CN104403028A (en) * | 2014-11-19 | 2015-03-11 | 中国科学院化学研究所 | Polypropylene catalyst containing carbonic ester external electron donor |
| CN104403028B (en) * | 2014-11-19 | 2017-04-12 | 中国科学院化学研究所 | Polypropylene catalyst containing carbonic ester external electron donor |
| CN106045994A (en) * | 2016-06-12 | 2016-10-26 | 上海大学 | Perfluoroalkyl indolizine derivative and synthesis method thereof |
| US11530281B2 (en) | 2016-08-19 | 2022-12-20 | Institute Of Chemistry, Chinese Academy Of Sciences | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101423572B (en) | 2011-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101824106B (en) | Catalytic component for olefin polymerization and catalyst thereof | |
| EP2489685B1 (en) | Process for preparing a catalyst component for olefin polymerization | |
| CN104250321B (en) | Catalyst component for olefin polymerization and olefin polymerization catalysis and olefine polymerizing process | |
| CN101155838A (en) | Method for producing a propylene polymer having a very high melt flowability | |
| CN101993506B (en) | Preparation method of catalyst component for olefin polymerization and catalyst | |
| KR20160073986A (en) | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor | |
| CN101628951B (en) | Olefin polymerization solid catalytic component and catalyst thereof | |
| KR20180080349A (en) | Catalyst carrier for olefin polymerization, solid catalyst component and catalyst | |
| US20100222528A1 (en) | Catalyst for the polymerization of olefins | |
| CN101423572B (en) | Catalyst component for olefin polymerization and catalyst thereof | |
| CN101423571A (en) | Catalyst component for olefin polymerization and catalyst thereof | |
| CN102372805B (en) | Preparation method of ultrahigh-molecular-weight polyethylene catalyst | |
| CN101824108B (en) | Ziegler-Natta catalyst | |
| CN101423566B (en) | Solid catalyst component and catalyst thereof | |
| CN101423570B (en) | Spherical catalyst component for olefin polymerization and catalyst thereof | |
| CN101831016B (en) | Olefin polymerization catalytic component and catalyst thereof | |
| CN102268110B (en) | Olefine polymerization catalyst component | |
| CN102268109B (en) | Solid titanium catalyst for olefin polymerization | |
| CN101759816A (en) | Method for preparing a catalyst component for olefinic polymerization, and a catalyst component thereof | |
| CN102796213B (en) | Catalyst component and catalyst system for olefin polymerization, applications thereof and olefin polymerization method | |
| CN100513432C (en) | Catalyst component for olefinic polymerization and its catalyst | |
| CN108264589B (en) | Polypropylene catalyst component, preparation method thereof and polypropylene catalyst | |
| CN105985464A (en) | Olefin polymerization solid catalyst component and catalyst thereof | |
| CN101671409B (en) | Olefin polymerization solid catalyst | |
| CN101824105B (en) | Solid titanium catalytic component and catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 |