CN101824107A - Solid main catalyst for olefin polymerization - Google Patents
Solid main catalyst for olefin polymerization Download PDFInfo
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- CN101824107A CN101824107A CN200910079173A CN200910079173A CN101824107A CN 101824107 A CN101824107 A CN 101824107A CN 200910079173 A CN200910079173 A CN 200910079173A CN 200910079173 A CN200910079173 A CN 200910079173A CN 101824107 A CN101824107 A CN 101824107A
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- alkene
- dicyclo
- tetracarboxylic acid
- herbaceous plants
- big flowers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a solid main catalyst for olefin polymerization, which comprises magnesium, titanium, halogen and an electron donor, wherein the electron donor is selected from at least one tetrasuccinate compound with a bridge group, and the compound satisfies a structural formula (I). The steric regularity and the steric hindrance of the compound of the electron donor are more suitable for catalyzing olefin polymerization, and the catalytic activity thereof is higher. Products have highly isotactic regularity; and polypropylene with unequal normality can be obtained when the solid main catalyst is matched with other components of the catalyst.
Description
Technical field
The present invention relates to a kind of solid main catalyst that is used for olefinic polymerization, be specifically related to a kind of solid main catalyst that contains the polyester compound, be specially adapted to propylene polymerization, can obtain high yield and high normal polypropylene.
Background technology
Polypropylene is a kind with fastest developing speed in the synthetic resins, occupies outstanding status in synthetic resins.At present, nearly all polypropylene product all is to be obtained by Ziegler-Natta (Z-N) catalyst propylene polymerization, and development that we can say catalyzer has promoted polypropylene catalyst and constantly updated.The Z-N catalyzer has passed through the development of several generations, and main research work concentrates on the electron donor compound more, and polytype electron donor compound occurred.
Disclosed electron donor compound comprises carboxylicesters, acid anhydrides, ketone, ether, alcohol, amine etc. and derivative thereof.In the disclosed olefin polymerization catalyst components of CN1042547A and CN1143651A, adopted 1, the 3-diether compound is as internal electron donor, and for example 2,2-diisopropyl alkene-1,3-Propanal dimethyl acetal and 9,9-two (methoxyl methyl) fluorenes; A kind of phthalate compound is disclosed among the CN85100097.
The succinate compounds is more as the patent report of internal electron donor, as CN1681853, CN1398270, CN1313869 and US0050014631, it not only can improve catalyst activity and polymkeric substance degree of isotacticity as internal electron donor, can also obtain the polymkeric substance of relative molecular weight wider distribution, be specially adapted to the polyolefinic production of copolymerization.Disclose a kind of ingredient of solid catalyst that contains four ester compounds four (benzoyloxy methyl) methane of specific type among the ZL02100900.7, this ingredient of solid catalyst can obtain the polymkeric substance of high yield when propylene polymerization.But four (benzoyloxy methyl) methane is molecular skeleton with the tetramethylolmethane, and it is not high that its space structure causes containing the polymkeric substance degree of isotacticity that the solid catalyst of this four ester cpds obtains.
Summary of the invention
The object of the invention provides a kind of high activity olefin polymerization, particularly the propylene polymerization solid Primary Catalysts.
Primary Catalysts of the present invention comprises magnesium, titanium, halogen and electron donor, and electron donor wherein is selected from least a succsinic acid four ester cpds that have abutment, and structural formula satisfies (I):
Substituent R in the formula
1, R
2Identical or different, be selected from H, halogen atom, C
1～C
20Straight or branched alkyl, C
3～C
20Cycloalkyl, C
6～C
20Aryl or C
7～C
20Aralkyl; Substituent R is selected from C
1～C
20Straight or branched alkyl, C
3～C
20Cycloalkyl, C
6～C
20Aryl or C
7～C
20Aralkyl.
Satisfy electron donor compound of the present invention and can be selected from following arbitrary compound:
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two isobutyl fat
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two ring pentyl esters
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester
7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two ring pentyl esters
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls
7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7,8-diethyl ester-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7,8-diethyl ester-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7,8-diethyl ester-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
7,8-diethyl ester-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7,8-diethyl ester-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls
7,8-diethyl ester-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
The preparation of electron donor compound can be adopted prior art, realizes by the esterification of acid anhydrides with alcohol.As with reference to " organic synthesis " (Wang Baoren, Science Press Beijing, method 1981-1985.), with dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride is dissolved in the alcoholic solvent that structural formula is ROH, wherein R is an alkyl or aryl; Add p-methyl benzenesulfonic acid again, reflux 24～100 hours, preferred 48～90 hours, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the mol ratio of 6-tetracarboxylic dianhydride and p-methyl benzenesulfonic acid is 100: 1～50, preferred 100: 1～10; Except that after desolvating, obtain the electron donor compound after washing, extraction, the drying.
The acquisition of titanium, magnesium, halogen is all extensively open in the prior art in the Primary Catalysts.Can pass through spherical magnesium halide alcohol adduct Mg (OR ') as magnesium and halogen
mX
(2-m)N (R
2OH) provide, R ' is C in the formula
1～C
20Alkyl, aralkyl or aryl; X is a halogen; M is the integer of 0≤m＜2; N is the decimal or the integer of 0＜n＜5; R
2Be C
1～C
20Alkyl, aralkyl or aryl; Spherical magnesium halide alcohol adduct size-grade distribution is 50～250 μ m.Magnesium halide specifically is selected from least wherein a kind of of magnesium chloride, magnesium bromide, chloro magnesium methylate or chloro magnesium ethylate, preferred magnesium chloride.Used alcohol is selected from least wherein a kind of of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols or isopropylcarbinol, preferred alcohol.
After the preparation of magnesium halide alcohol adduct can adopt magnesium halide and alcohol to be total to heating for dissolving, high pressure ejection or high-speed stirring were solidified into microsphere particle and obtain, specifically referring to the associated description among the CN1110281A in heat-eliminating medium.
Titanium in the Primary Catalysts is Ti (OR) by general formula
nX
(4-n)Compound provide, R is C in the formula
1～C
20Alkyl, aryl or aralkyl; X is a halogen; N is the integer of 0≤n＜4.Titanium compound is selected from least wherein a kind of of purity titanium tetraethoxide, four titanium butoxide, chloro tri-alkoxy titanium, dichloro dialkoxy titanium, trichlorine titan-alkoxide, titanium tetrachloride or titanium tetrabromide, preferred titanium tetrachloride.
The quality group of each component becomes in the described Primary Catalysts:
Electron donor compound 1～10%
Titanium 1～15%
Magnesium 10～25%
Halogen 40～60%
Solid main catalyst agent of the present invention can be selected following method preparation:
At first, spherical magnesium halide alcohol adduct particle is joined-50～20 ℃, in preferred-30～0 ℃ the halogenated titanium liquid, reacted 1～6 hour, preferred 1～4 hour, the mol ratio of magnesium and titanium was 1: 5～1: 100, preferred 1: 10～1: 50; Be warming up to 30～80 ℃ then, add the electron donor compound after preferred 40～60 ℃; Be warming up to 100～140 ℃ again, preferred 110～130 ℃, reacted 1～6 hour, preferred 1～4 hour, the mol ratio of magnesium and electron donor compound was 2: 1～20: 1, preferred 2: 1～12: 1; Add the halogenated titanium liquid with the first step same amount after the filtration again, in 100～140 ℃ of reactions 1～4 hour, more after filtration, obtain solid main catalyst after the washing, drying.
When solid main catalyst of the present invention is used for propylene polymerization, also need to add alkylaluminium cpd.The aluminum alkyls general formula is AlR
nX
(3-n)R is C in the formula
1～C
20Alkyl, aryl or aralkyl; X is a halogen; N is the integer of 0≤n≤3.Specifically be selected from a kind of in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride or the chloro-di-isobutyl aluminum, preferred triethyl aluminum or triisobutyl aluminium.
The catalyzing propone polymerization can be adopted disclosed the whole bag of tricks, and there is no particular limitation, and polymerization temperature is generally 0～80 ℃, preferred 40～60 ℃.Each amount ratio between forming of catalyzer is by titanium during polymerization: aluminium: the molar ratio computing of silicon is 1: 1～2000: 1～50; Preferred 1: 1～500: 1～30.
Compared with prior art, in the Primary Catalysts provided by the invention, the electron donor compound is the new multicomponent succinate compounds that has polynuclear plane, by the special construction of its abutment and changeable ester group structure, its space regularity and sterically hinderedly more be applicable to the catalyzing propone polymerization, catalytic activity is higher, and product has high taxis, other is formed to cooperate catalyzer, can obtain the polypropylene of different degree of isotacticity.
Embodiment
Embodiment 1:
(1) dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid dimethyl ester
With 10g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL methanol solvate, add the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 80 ℃, decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 8.2g white crystal dicyclo (2,2 after the drying again, 2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 3.39 (s, 12H, CH
3); δ 2.96 (m, 4H, CH); δ 2.37 (m, 2H, CH); δ 5.59 (m, 2H, CH).
(2) preparation of Primary Catalysts
Under the anhydrous and oxygen-free condition, (make by oneself, preparation process is with document CN1110281A, and mean particle size is 110 μ m, and specific surface is 150-230M with 5.0 gram microspheroidal magnesium chloride alcohol adduct particles
2/ g, alcohol is 2.85: 1 with the molar ratio of content of magnesium chloride, molecular formula: MgCl
22.85CH
3CH
2OH) join in 140 milliliters of titanium tetrachloride liquid of-20 ℃, react after 2 hours, be warming up to 60 ℃ gradually; Add 1.26 gram 9 dicyclos (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester is warming up to 120 ℃ gradually, reacts 2 hours, filters; Add 140 milliliters of titanium tetrachlorides again, in 120 ℃ of reactions 2 hours and filtration.In 60 ℃ of washings 5 times, at room temperature use 50 milliliters of hexane wash once with 100 milliliters of hexanes, obtain solid catalyst after the vacuum-drying.The quality percentage composition of each component is in the catalyzer: titanium 2.89%, electron donor compound 6.58%, magnesium 13.47%, chlorine 50.61%.
(3) propylene polymerization
Also use in nitrogen and the abundant metathetical reaction flask of propylene gas through vacuum drying treatment at 250 milliliters, add 100 milliliters of heptane of handling through anhydrous and oxygen-free, pressure is 1 normal atmosphere in the maintenance bottle, temperature is 50 ℃, add the 6mmol triethyl aluminum, stir after 5 minutes, add the above-mentioned solid catalyst of 0.1g.The mol ratio of titanium and triethyl aluminum is 1: 100 in the solid catalyst.Polyreaction 1 hour, with acidifying ethanol termination reaction, suction filtration is also used washing with alcohol, and vacuum-drying gets polymkeric substance.
Polymerization result is listed in table 1.
Embodiment 2:
(1) dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid diisopropyl fat ester
With 10g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL isopropanol solvent, add the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 100 ℃, decompression remove add again behind the Virahol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 8.0g white crystal dicyclo (2,2 after the drying again, 2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.27 (s, 24H, CH3); δ 2.18 (m, 4H, CH); δ 3.84 (m, 4H, CH); δ 5.59 (m, 2H, CH).
(2) preparation of Primary Catalysts
Except the electron donor compound changes 7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid diisopropyl ester 1.68 grams, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.54%, electron donor compound 6.18%, magnesium 13.57%, chlorine 50.21%.
(3) propylene polymerization
Except adding the 5.4mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Polymerization result is listed in table 1.
Embodiment 3:
(1) dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid dibenzyl ester
With 10g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL benzylalcohol solvent, add the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 100 ℃, decompression remove add again behind the Virahol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 8.1g white crystal dicyclo (2,2 after the drying again, 2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 4.12 (m, 8H, CH
2); δ 2.18 (m, 4H, CH); δ 2.78 (m, 2H, CH); δ 5.59 (m, 2H, CH); δ 7.26 (m, 10H, C
6H
5).
(2) preparation of Primary Catalysts
Except the electron donor compound changes dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dibenzyl ester 2.38 grams, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.24%, electron donor compound 6.28%, magnesium 14.57%, chlorine 51.21%.
(3) propylene polymerization
Except adding the 4.7mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Polymerization result is listed in table 1.
Embodiment 4:
(1) 7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid dimethyl ester
With 10g7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL methanol solvate, add the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 80 ℃, decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 8.5g white crystal 7-methyl-dicyclo (2,2 after the drying again, 2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.71 (m, 1H, CH
3); δ 3.39 (s, 12H, CH
3); δ 2.55 (m, 4H, CH); δ 2.37 (m, 2H, CH); δ 5.31 (m, 1H, CH).
(2) preparation of Primary Catalysts
Except the electron donor compound changes 7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester 1.31 grams, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.11%, electron donor compound 6.28%, magnesium 19.28%, chlorine 49.61%.
(3) propylene polymerization
Except adding the 4.4mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Embodiment 5:
(1) 7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid dibenzyl ester
With 10g7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL benzylalcohol solvent, add the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 80 ℃, decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 7.2g white crystal 7-methyl-dicyclo (2,2 after the drying again, 2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.71 (m, 1H, CH
3); δ 4.12 (m, 8H, CH
2); δ 2.33 (m, 4H, CH); δ 2.78 (m, 2H, CH); δ 5.37 (m, 1H, CH); δ 7.26 (m, 20H, C
6H
5).
(2) preparation of Primary Catalysts
Except the electron donor compound changes 7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dibenzyl ester 2.4 grams, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.13%, electron donor compound 6.27%, magnesium 19.29%, chlorine 49.65%.
(3) propylene polymerization
Except adding the 4.4mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Embodiment 6:
(1) 7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid dimethyl ester
With 10g7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL methanol solvate, add the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 80 ℃, decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 8.6g white crystal 7-ethyl-dicyclo (2,2 after the drying again, 2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.06 (m, 3H, CH
3); δ 3.50 (s, 12H, CH
3); δ 2.33 (m, 4H, CH); δ 2.00 (m, 2H, CH); δ 5.37 (m, 1H, CH).
(2) preparation of Primary Catalysts
Except the electron donor compound changes 7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester 1.37 grams, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.15%, electron donor compound 6.58%, magnesium 19.70%, chlorine 48.51%.
(3) propylene polymerization
Except adding the 4.5mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Embodiment 7:
(1) 7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid two cyclohexyls
With 10g7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL hexalin solvent, add the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 80 ℃, decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 7.3g white crystal 7-ethyl-dicyclo (2,2 after the drying again, 2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls.
1HNMR (CDCl
3, 300MHz) analytical results: δ 1.44 (s, 40H, C
6H
10); δ 3.50 (s, 4H, CH); δ 3.38 (m, 2H, CH); δ 5.37 (m, 1H, CH); δ 2.00 (m, 2H, CH
2); δ 1.06 (m, 3H, CH
3).
(2) preparation of Primary Catalysts
Except the electron donor compound changes 7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester 2.57 grams, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.45%, electron donor compound 6.68%, magnesium 20.70%, chlorine 49.51%.
(3) propylene polymerization
Except adding the 5.4mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Embodiment 8:
(1) 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid dimethyl ester
With 10g7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL methanol solvate, add the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 80 ℃, decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 7.6g white crystal 7-chloro-dicyclo (2,2 after the drying again, 2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 3.39 (s, 12H, CH
3); δ 2.55 (m, 4H, CH); δ 2.37 (m, 2H, CH); δ 5.31 (m, 1H, CH).
(2) preparation of Primary Catalysts
Except the electron donor compound changes 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester 1.39 grams, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.54%, electron donor compound 6.89%, magnesium 20.54%, chlorine 52.14%.
(3) propylene polymerization
Except adding the 5.3mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Embodiment 9:
(1) 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid dibenzyl ester
With 10g7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL benzylalcohol solvent, add the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 80 ℃, decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 7.0g white crystal 7-chloro-dicyclo (2,2 after the drying again, 2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 4.12 (m, 8H, CH
2); δ 2.18 (m, 4H, CH); δ 2.78 (m, 2H, CH); δ 5.59 (m, H, CH); δ 7.26 (m, 10H, C
6H
5).
(2) preparation of Primary Catalysts
Except the electron donor compound changes 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester 2.42 grams, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.34%, electron donor compound 7.89%, magnesium 21.54%, chlorine 50.14%.
(3) propylene polymerization
Except adding the 4.9mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Embodiment 10:
(1) 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
With 10g7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL methanol solvate, add the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 80 ℃, decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 6.5g white crystal 7-phenyl-dicyclo (2,2 after the drying again, 2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 3.50 (s, 12H, CH
3); δ 2.33 (m, 4H, CH); δ 2.78 (m, 2H, CH); δ 5.37 (m, 1H, CH); δ 7.26 (s, 5H, C
6H
5).
(2) preparation of Primary Catalysts
Except the electron donor compound changes 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester 1.19 grams, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.67%, electron donor compound 7.15%, magnesium 19.89%, chlorine 50.69%.
(3) propylene polymerization
Except adding the 5.6mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Embodiment 11:
(1) 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two ring pentyl esters
With 10g7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL cyclopentanol solvent, add the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 80 ℃, decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 6.3g white crystal 7-phenyl-dicyclo (2,2 after the drying again, 2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two ring pentyl esters.
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.51 (s, 32H, C
5H
8); δ 3.50 (s, 4H, CH); δ 2.78 (m, 4H, CH); δ 3.38 (m, 1H, CH); δ 5.37 (m, 1H, CH); δ 7.26 (s, 5H, C
6H
5).
(2) preparation of Primary Catalysts
Except the electron donor compound changes 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid two ring pentyl esters 2.01 grams, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.65%, electron donor compound 7.05%, magnesium 20.19%, chlorine 49.69%.
(3) propylene polymerization
Except adding the 5.5mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Embodiment 12:
(1) 7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
With 10g7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (AlfaAesar reagent) is dissolved in the 80mL methanol solvate, adds the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 80 ℃, decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 6.7g white crystal 7 after the drying again, 8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.71 (s, 6H, CH
3); δ 3.66 (s, 12H, CH
3); δ 2.33 (m, 4H, CH); δ 2.78 (m, 2H, CH).
(2) preparation of Primary Catalysts
Except the electron donor compound changes 7 into, 8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 1.37 grams, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.55%, electron donor compound 6.95%, magnesium 20.13%, chlorine 49.59%.
(3) propylene polymerization
Except adding the 5.3mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Embodiment 13:
(1) 7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
With 10g7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic dianhydride (AlfaAesar reagent) is dissolved in the 80mL benzylalcohol solvent, adds the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 80 ℃, decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium bicarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 5.7g white crystal 7 after the drying again, 8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.71 (m, 6H, CH
3); δ 3.38 (m, 2H, CH); δ 2.33 (m, 4H, CH); δ 4.12 (m, 8H, CH
2); δ 7.26 (m, 20H, C
6H
5).
(2) preparation of Primary Catalysts
Except the electron donor compound changes 7 into, 8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester 2.67 grams, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.68%, electron donor compound 6.85%, magnesium 21.13%, chlorine 52.59%.
(3) propylene polymerization
Except adding the 5.6mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
The comparative example 1:
The preparation method of solid main catalyst and propene polymerizing method just replace dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester with diisobutyl phthalate with embodiment 1 in the solid catalyst preparation process.Test-results is as shown in table 1.
The comparative example 2:
The preparation method of solid main catalyst and propene polymerizing method be with embodiment 1, just in the solid catalyst preparation process with 2,3-di-isopropyl succsinic acid diethyl ester replacement dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester.Test-results is as shown in table 1.
The comparative example 3:
The preparation method of solid main catalyst and propene polymerizing method be with embodiment 1, just in the solid catalyst preparation process with 9,9-pair of (methoxyl methyl) fluorenes (ACROS reagent).Test-results is as shown in table 1.
The comparative example 4:
The preparation method of solid main catalyst and propene polymerizing method are with four (benzoyloxy methyl) methane (referring to Chinese patent CN1169845C) in the solid catalyst preparation process with embodiment 1.
Synthesizing of four (benzoyloxy methyl) methane: add 100mLTHF in the 10g tetramethylolmethane, under agitation add the 25mL pyridine, slowly add the 35mL Benzoyl chloride again, at room temperature stirred 1 hour, refluxed 8 hours.With the molten water-toluene extraction of reactant, organic phase is washed 2 times with saturated common salt, anhydrous magnesium sulfate drying.Desolventize, obtain white solid.
1H NMR (CDCl
3, 300MHz) analytical results: δ 4.77 (s, 8H, CH
2); δ 7.30-8.00 (m, 20H, C
6H
5).
Test-results is as shown in table 1.
The polymerizing condition of table 1 embodiment and Comparative Examples and experimental result
Claims (9)
1. an olefin polymerization solid Primary Catalysts comprises magnesium, titanium, halogen and electron donor, it is characterized in that electron donor is selected from least a succsinic acid that has abutment four ester cpds that satisfy structural formula (I):
Substituent R in the formula
1, R
2Identical or different, be selected from H, halogen atom, C
1～C
20Straight or branched alkyl, C
3～C
20Cycloalkyl, C
6～C
20Aryl or C
7～C
20Aralkyl; Substituent R is selected from C
1～C
20Straight or branched alkyl, C
3～C
20Cycloalkyl, C
6～C
20Aryl or C
7～C
20Aralkyl.
2. Primary Catalysts according to claim 1 is characterized in that the electron donor compound is selected from following arbitrary compound:
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two isobutyl fat
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two ring pentyl esters
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls
Dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls
7-methyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester
7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
7-ethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two ring pentyl esters
7-sec.-propyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls
7,8-dimethyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7,8-diethyl ester-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7,8-diethyl ester-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7,8-diethyl ester-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
7,8-diethyl ester-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7,8-diethyl ester-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls
7,8-diethyl ester-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diethyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-propyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisopropyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid di-n-butyl
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid diisobutyl ester
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid two cyclohexyls
7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester.
3. Primary Catalysts according to claim 1, magnesium in it is characterized in that forming and halogen are by spherical magnesium halide alcohol adduct Mg (OR ')
mX
(2-m)N (R
2OH) provide, R ' is C in the formula
1～C
20Alkyl, aralkyl or aryl; X is a halogen; M is the integer of 0≤m＜2; N is the decimal or the integer of 0＜n＜5; R
2Be C
1～C
20Alkyl, aralkyl or aryl; Spherical magnesium halide alcohol adduct size-grade distribution is 50～250 μ m.
4. Primary Catalysts according to claim 3 is characterized in that magnesium halide is selected from least wherein a kind of of magnesium chloride, magnesium bromide, chloro magnesium methylate or chloro magnesium ethylate; Used alcohol is selected from least wherein a kind of of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols or isopropylcarbinol.
5. Primary Catalysts according to claim 4 is characterized in that magnesium halide is a magnesium chloride, and used alcohol is ethanol.
6. Primary Catalysts according to claim 1, the titanium in it is characterized in that forming is Ti (OR) by general formula
nX
(4-n)Compound provide, R is C in the formula
1～C
20Alkyl, aryl or aralkyl; X is a halogen; N is the integer of 0≤n＜4.
7. Primary Catalysts according to claim 6 is characterized in that titanium compound in the catalyzer is selected from least wherein a kind of of purity titanium tetraethoxide, four titanium butoxide, chloro tri-alkoxy titanium, dichloro dialkoxy titanium, trichlorine titan-alkoxide, titanium tetrachloride or titanium tetrabromide.
8. Primary Catalysts according to claim 7 is characterized in that titanium compound is a titanium tetrachloride.
9. the Primary Catalysts one of described according to claim 1-8 is characterized in that the quality group of each component becomes:
Electron donor compound 1～10
Titanium 1～15
Magnesium 10～25%
Halogen 40～60%.
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| CN103539874A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Solid titanium catalyst for olefin polymerization, and preparation method thereof |
| CN103694385A (en) * | 2012-09-28 | 2014-04-02 | 中国石油天然气股份有限公司 | Propylene polymerization catalytic component and catalyst thereof |
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| US6818583B1 (en) * | 1999-04-15 | 2004-11-16 | Basell Poliolefine Italia S.P.A. | Components and catalysts for the polymerization of olefins |
| CA2396232C (en) * | 2000-10-13 | 2011-09-20 | Basell Poliolefine Italia S.P.A. | Catalyst components for the polymerization of olefins |
| US7005487B2 (en) * | 2002-07-02 | 2006-02-28 | Basell Poliolefine Italia S.R.L. | Catalyst system for the polymerization of olefins |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103539874A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Solid titanium catalyst for olefin polymerization, and preparation method thereof |
| CN103539874B (en) * | 2012-07-12 | 2016-02-10 | 中国石油天然气股份有限公司 | Olefin polymerization solid titanium catalyst and preparation method thereof |
| CN103694385A (en) * | 2012-09-28 | 2014-04-02 | 中国石油天然气股份有限公司 | Propylene polymerization catalytic component and catalyst thereof |
| CN103694385B (en) * | 2012-09-28 | 2016-03-09 | 中国石油天然气股份有限公司 | Propylene polymerization catalytic component and catalyzer thereof |
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