CN101195668A - Load type main catalyst for propylene polymerization and method for producing the same - Google Patents
Load type main catalyst for propylene polymerization and method for producing the same Download PDFInfo
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- CN101195668A CN101195668A CNA2006101648182A CN200610164818A CN101195668A CN 101195668 A CN101195668 A CN 101195668A CN A2006101648182 A CNA2006101648182 A CN A2006101648182A CN 200610164818 A CN200610164818 A CN 200610164818A CN 101195668 A CN101195668 A CN 101195668A
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- dihydroanthracene
- succinic acid
- succinate
- methyl
- chloro
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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 supported main catalyst of propone polymerization. The relative donor compound is represented as following, wherein the donor arranges a new succinate compound with large substituent group and helical structure on molecular skeleton, therefore, the inventive main catalyst has high catalytic activity to catalyze propone polymerization, the product polypropylene has high stereoregularity, and while assisted with promoter, the catalyst can obtain polypropylene with different regularities. The invention further discloses a preparation method of the main catalyst.
Description
Technical field
The present invention relates to load type main catalyst for propylene polymerization and preparation method thereof, be specifically related to load type main catalyst that contains succinate class internal electron donor compound and preparation method thereof.
Background technology
The internal electron donor compound is as one of important component of Ziegler-Natta catalyst, and the improvement of catalyst performance is played crucial effects.It not only can improve activity of such catalysts, also can improve the orientation property of catalyzer simultaneously, makes polymerisate have high taxis.
1, the invention of 3-two ethers electron donor compounds makes the catalytic activity of catalyzer, the degree of isotacticity of polymkeric substance etc. obtain significant raising.People are to different 1, the performance of the structure of 3-two ethers electron donor compounds and the catalyzer that obtains has thus been carried out detailed research, and applied for many patents, and as: CN1473809, CN1376722, CN1298887, CN1268957, CN1143651, CN1141303, CN1141285, CN1066723; EP0728770, EP0728724, EP0361493, US5095153, US5068213, US4978648 etc.Result of study shows, 1, and the raising that substituting group that spatial volume is bigger on 2 carbon atoms in the 3-two ethers electron donor compounds and the higher substituting group of symmetry help catalytic activity and polymkeric substance degree of isotacticity.
In recent years, the succinate compounds has caused people's extensive interest as novel electron donor.Prosposition is chiral carbon atom or the succinate compounds that the has different substituents road that appears in the newspapers in patent more on the molecular skeleton.As CN1681853, CN1398270, CN1313869, US0050014631, WO00/63261, WO2004024785 etc.With the diether compound is the catalyzer of electron donor, and its olefinic polymerization product has the molecular weight distribution of relative narrower, and with succinate class electron donor catalyst, can obtain the polymkeric substance of relative molecular weight wider distribution.
WO00/63261 and CN1313869 have described with succinate or have replaced the catalyzer of succinate compounds as the preparation of internal electron donor component, have high reactivity when being used for propylene polymerization, and the product polypropylene has high taxis.US0050014631 has described the succinate class catalyzer of loading type, compares with unsupported catalyst, has higher activity, and polymerisate has higher taxis.
Summary of the invention
The purpose of this invention is to provide a kind of propylene polymerization Primary Catalysts that comprises ad hoc structure succinate class electron donor, another object of the present invention provides the preparation method of above-mentioned Primary Catalysts.
In conjunction with people to 1, the achievement in research of 3-two ethers and succinate class electron donor, the contriver thinks and has the high succinate class electron donor compound of big substituted radical and structural symmetry as catalyst component, can further improve the taxis of catalytic activity and polymkeric substance.
Therefore, the Primary Catalysts that the present invention proposes mainly is made up of spherical magnesium halide alcohol adduct, halogenated titanium, electron donor compound, it is characterized in that the electron donor compound has following structure:
Substituent R in the formula
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Identical 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 in the formula
9, R
10Identical or different, be selected from C
1～C
20Straight or branched alkyl, C
3～C
20Cycloalkyl, C
6～C
20Aryl or C
7～C
20Aralkyl; Each composition weight of Primary Catalysts consists of:
Electron donor compound 1-10%
Titanium 1-15%
Magnesium 10-25%
Halogen 40-60%.
Above-mentioned electron donor compound synthetic is that preferred 2～6 hours, the mol ratio of anthracene or derivatives thereof and maleic anhydride was 1: (1～2), preferred 1: (1.1～1.5) with anthracene or derivatives thereof and maleic anhydride reflux 1～8 hour in organic solvent; Be cooled to room temperature, place and separate out crystallization, filtration, drying; Get solid chemical compound in alcoholic solvent, add p-methyl benzenesulfonic acid, the mol ratio of anthracene and p-methyl benzenesulfonic acid is 100: (1～50), preferred 100: (1～10); Reflux 24～100 hours, preferred 48～90 hours; Except that after desolvating, obtain after washing, extraction, the drying.
Satisfy electron donor compound of the present invention and can be selected from following arbitrary compound:
9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
9,10-dihydroanthracene-9,10-α, β-diethyl succinate
9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
1-methyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
1-methyl-9,10-dihydroanthracene-9,10-α, β-diethyl succinate
1-methyl-9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
1-methyl-9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
1-methyl-9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
1-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
1-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
1-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
1-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
2-methyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
2-methyl-9,10-dihydroanthracene-9,10-α, β-diethyl succinate
2-methyl-9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
2-methyl-9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
2-methyl-9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
2-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
2-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
2-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
2-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
2-ethyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
2-ethyl-9,10-dihydroanthracene-9,10-α, β-diethyl succinate
2-ethyl-9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
2-ethyl-9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
2-ethyl-9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
2-ethyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
2-ethyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
2-ethyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
2-ethyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-diethyl succinate
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
1-chloro-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
1-chloro-9,10-dihydroanthracene-9,10-α, β-diethyl succinate
1-chloro-9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
1-chloro-9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
1-chloro-9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
1-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
1-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
1-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
1-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
2-chloro-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
2-chloro-9,10-dihydroanthracene-9,10-α, β-diethyl succinate
2-chloro-9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
2-chloro-9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
2-chloro-9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
2-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
2-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
2-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
2-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
Size-grade distribution 50～250 μ m of the magnesium halide alcohol adduct carrier during catalyzer is formed, its general formula are Mg (OR ')
mX
(2-m)N (R
2OH), 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.Magnesium halide specifically is selected from wherein a kind of of magnesium chloride, magnesium bromide, chloro magnesium methylate or chloro magnesium ethylate, preferred magnesium chloride.Used alcohol is selected from wherein a kind of of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols or isopropylcarbinol, preferred alcohol.
After the preparation of magnesium halide alcohol adduct adopted 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 in heat-eliminating medium, and concrete steps are referring to the associated description among the CN1110281A.
Catalyst component halogenated titanium general formula is Ti (OR)
nX
(4-n), R is C in the formula
1-C
20Alkyl, aryl or aralkyl; X is a halogen; N is the integer of 0≤n＜4.Specifically be selected from 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.
Primary Catalysts of the present invention synthetic be by after spherical magnesium halide alcohol adduct and the halogenated titanium reaction, obtains with the internal electron donor compound effects again.Concrete steps are: 1) 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; 2) be warming up to 30～80 ℃, add the electron donor compound after preferred 40～60 ℃; 3) 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; 4) add halogenated titanium liquid with step (1) same amount after filtering again, in 100～140 ℃ of reactions 1～4 hour, more after filtration, obtain Primary Catalysts after the washing, drying.
Primary Catalysts provided by the invention also needs with addition of the promotor alkylaluminium cpd when being used for propylene polymerization.Its general formula is A1RnX
(3-n)R is alkyl, the aryl or aralkyl of C1～C20 in the formula; 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 titanium in the catalyst system and the mol ratio of the aluminium in the promotor are 1: 1～1: 2000, are preferably 1: 1～1: 500.
For obtaining better polymerization effect, when using Primary Catalysts provided by the invention, except that alkylaluminium cpd, also need further with addition of alkoxy-silicon compound.Wherein a kind of as dimethoxy dimethyl-silicon, diethoxy dimethyl-silicon or dimethoxy phenylbenzene silicon, preferred dimethoxy phenylbenzene silicon, the mol ratio of silicon is 1: 1～1: 50 in titanium in the Primary Catalysts and the dimethoxy phenylbenzene silicon, preferred 1: 1～1: 20.
Primary Catalysts catalyzing propone provided by the invention polymerization can be adopted the whole bag of tricks of the prior art, and there is no particular limitation, and polymerization temperature is generally 0～80 ℃, preferred 40～60 ℃.Only be example with the slurry polymerization herein, the use that the brief description catalyzer is basic: also use in nitrogen and the abundant metathetical reactor 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; Add promotor triethyl aluminum and dimethoxy phenylbenzene silicon, stir after 5 minutes, add Primary Catalysts; Polyreaction 1 hour; With acidifying ethanol termination reaction, suction filtration is also used washing with alcohol, and vacuum-drying gets polymkeric substance.
Compared with prior art, electron donor has adopted the novel succinate compounds that has large-substituent group, spirane structure on the molecular skeleton in the Primary Catalysts provided by the invention, have high catalytic activity during the catalyzing propone polymerization, the product polypropylene has high taxis simultaneously.Cooperate promotor again, can obtain the polypropylene of different degree of isotacticity.
Embodiment
Synthesizing of embodiment 1 electron donor: 9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
In 150mL dimethylbenzene, add the 6.0g anthracene, the 3.36g maleic anhydride was in 150 ℃ of reflux 4 hours; Be cooled to room temperature, placement, slowly separate out crystallization, filtration, vacuum-drying, obtain 8.09g white crystal 9,10-dihydroanthracene-9,10-α, β-Succinic anhydried; Measure fusing point: 228 ℃,
1H NMR (CDCl
3, 300MHz) analytical results: δ 3.54 (s, 2H, CH); δ 4.83 (s, 2H, CH); δ 7.30 (m, 8H, ph-H).
Get 8.09g 9,10-dihydroanthracene-9,10-α, β-Succinic anhydried place the 80mL anhydrous methanol, add the 0.10g p-methyl benzenesulfonic acid, reflux 60 hours in 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 5.31g white crystal 9 after the drying again, 10-dihydroanthracene-9,10-α, β-dimethyl succinate.Measure fusing point: 155 ℃,
1HNMR (CDCl
3, 300MHz) analytical results: δ 3.21 (s, 2H, CH); δ 3.51 (s, 6H, CH
3); δ 4.60 (s, 2H, CH); δ 7.13 (m, 4H, ph-H); δ 7.31 (m, 4H, ph-H).
Synthesizing of embodiment 2 electron donors: 9,10-dihydroanthracene-9,10-α, β-diethyl succinate intermediate 9,10-dihydroanthracene-9,10-α, the synthetic method of β-Succinic anhydried is with embodiment 1.
Get 6.12g 9,10-dihydroanthracene-9,10-α, β-Succinic anhydried place the 60mL dehydrated alcohol, add the 0.10g p-methyl benzenesulfonic acid, reflux 80 hours in 90 ℃; Decompression remove add behind the ethanol 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 6.11g white crystal 9 after the drying again, 10-dihydroanthracene-9,10-α, β-diethyl succinate.Measure fusing point: 85 ℃,
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.10 (t, 3H, CH
3); δ 3.20 (s, 2H, CH); δ 3.95 (m, 4H, CH
2); δ 4.60 (s, 2H, CH); δ 7.12 (m, 4H, ph-H); δ 7.31 (m, 4H, ph-H).
Synthesizing of embodiment 3 electron donors: 9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid intermediate 9,10-dihydroanthracene-9,10-α, the synthetic method of β-Succinic anhydried is with embodiment 1.
Get 6.51g 9,10-dihydroanthracene-9,10-α, β-Succinic anhydried place the 60mL Virahol, add the 0.10g p-methyl benzenesulfonic acid, reflux 80 hours in 100 ℃; Decompression is removed and is added 50mL behind the Virahol and contain the aqueous solution of 0.1g sodium bicarbonate, obtain 6.48g white crystal 9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, after filtering, remove ether.Measure fusing point: 262 ℃,
1H NMR (CDCl
3, 300MHz) analytical results: δ 1.08 (m, 12H, CH
3); δ 3.19 (m, 2H, CH); δ 4.58 (d, 2H, CH); δ 4.80 (m, 2H, CH); δ 7.12 (m, 4H, ph-H); δ 7.30 (m, 4H, ph-H).
Embodiment 4 electron donors synthetic-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester intermediate 9,10-dihydroanthracene-9,10-α, the synthetic method of β-Succinic anhydried is with embodiment 1.
Get 3.97g 9,10-dihydroanthracene-9,10-α, β-Succinic anhydried place the 30mL isopropylcarbinol, add the 0.10g p-methyl benzenesulfonic acid, reflux 80 hours in 100 ℃; Decompression remove add the 80mL saturated sodium bicarbonate aqueous solution behind the isopropylcarbinol, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 3.82g white crystal 9 after the drying again, 10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester.Measure fusing point: 52.5 ℃,
1H NMR (CDCl
3, 300MHz) analytical results: δ 0.86 (m, 12H, CH
3); δ 1.78 (m, 2H, CH); δ 3.26 (s, 2H, CH); δ 3.61 (m, 2H, CH); δ 3.76 (m, 2H, CH); δ 4.61 (s, 2H, CH); δ 7.13 (m, 4H, ph-H); δ 7.303 (m, 4H, ph-H).
Embodiment 5 1-methyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate synthetic
Except that anthracene replaced with 1-methylanthracene 6.5g, all the other operation stepss were with embodiment 1.Obtain 7.9g 1-methyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate.
Embodiment 6 2-methyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate synthetic
Except that anthracene was used 2-methyl anthracene 6.5g, all the other operation stepss were with embodiment 1.Obtain 8.5g2-methyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate.
Embodiment 7 2-ethyls-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate synthetic
Except that anthracene was used 2-ethyl anthracene 7.0g, all the other operation stepss were with embodiment 1.Obtain 8.9g2-ethyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate.
Embodiment 8 2-tertiary butyls-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate is synthetic
Except that anthracene was used 2-tertiary butyl anthracene 7.9g, all the other operation stepss were with embodiment 1.Obtain 8.0g2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate.
Embodiment 9 1-chloro-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate synthetic
Except that anthracene was used 1-chrloroanthracene 7.2g, all the other operation stepss were with embodiment 1.Obtain 9.0g1-chloro-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate.
The preparation and the polymerization of embodiment 10 Primary Catalystss
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 1.0 grams 9,10-dihydroanthracene-9,10-α, β-dimethyl succinate 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 30 milliliters of hexane wash once with 100 milliliters of hexanes, obtain magnesium chloride load type Primary Catalysts after the vacuum-drying.The content of each component is in the catalyzer: titanium 3.82%, electron donor compound 9.85%, magnesium 13.47%, chlorine 50.61%.
Slurry 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 4 milliliters of triethyl aluminums, stir after 5 minutes, add the above-mentioned Primary Catalysts of 0.1g.The mol ratio of the aluminium in the Primary Catalysts in titanium and the promotor is 1: 100.Polyreaction 1 hour, with acidifying ethanol termination reaction, suction filtration is also used washing with alcohol, and vacuum-drying gets polymkeric substance.
The polymerization relevant data is listed in table 1.
The comparative example 1
Preparation of catalysts method and propene polymerizing method be with embodiment 10, just in catalyst preparation process with 2,3-di-isopropyl succsinic acid diethyl ester replacement 9,10-dihydroanthracene-9,10-α, β-dimethyl succinate.Test-results is as shown in table 1.
The comparative example 2
Preparation of catalysts method and propene polymerizing method be with embodiment 10, just in catalyst preparation process with 2, (ACROS reagent company provides 3-di-isopropyl dibutyl succinate, preparation is referring to JP2005306918A) replace 9,10-dihydroanthracene-9,10-α, β-dimethyl succinate.Test-results is as shown in table 1.
The comparative example 3
Preparation of catalysts method and propene polymerizing method are with embodiment 10, be with 2 in catalyst preparation process, (ACROS reagent company provides 3-di-isopropyl di-iso-octyl succinate, preparation is referring to CN1721455A) replace 9 together with diisobutyl phthalate (FLUKA reagent company provides), 10-dihydroanthracene-9,10-α, β-dimethyl succinate.Test-results is as shown in table 1.
The preparation and the polymerization of embodiment 11 Primary Catalystss
The preparation of Primary Catalysts is with embodiment 10.
Slurry polymerization: after adding the promotor triethyl aluminum, add dimethoxy phenylbenzene silicon, the mol ratio of silicon is 10: 1 in aluminium in the triethyl aluminum and the dimethoxy phenylbenzene silicon, and all the other are with embodiment 10.The polymerization relevant data is listed in table 1.
The preparation and the polymerization of embodiment 12 Primary Catalystss
The preparation of Primary Catalysts: remove the internal electron donor compound and adopt 9,10-dihydroanthracene-9,10-α, outside β-diethyl succinate, all the other are with embodiment 10.The content of each component is in the catalyzer: titanium 2.25%, electron donor compound 4.06%, magnesium 13.89%, chlorine 47.18%.
Slurry polymerization is with embodiment 10.
The polymerization relevant data is listed in table 1.
The preparation and the polymerization of embodiment 13 Primary Catalystss
The preparation of Primary Catalysts is with embodiment 12.Slurry polymerization: with embodiment 11.
The polymerization relevant data is listed in table 1.
The comparative example 4
The Preparation of catalysts method is with embodiment 12, and propene polymerizing method is with embodiment 11, just in catalyst preparation process with 2,3-di-isopropyl succsinic acid diisobutyl ester replacement 9,10-dihydroanthracene-9,10-α, β-diethyl succinate.Test-results is as shown in table 1.
The comparative example 5
The Preparation of catalysts method is with embodiment 12, and propene polymerizing method is with 2 in catalyst preparation process with embodiment 11,3-di-isopropyl succsinic acid diisobutyl ester replaces 9 together with diisobutyl phthalate, 10-dihydroanthracene-9,10-α, β-diethyl succinate.Test-results is as shown in table 1.
The comparative example 6
The Preparation of catalysts method is with embodiment 12, and propene polymerizing method is with 2 in catalyst preparation process with embodiment 11,3-di-n-butyl ethyl succinate (ACROS reagent company provides, and preparation is referring to US6716939B2) replaces 9,10-dihydroanthracene-9,10-α, β-diethyl succinate.Test-results is as shown in table 1.
The comparative example 7
The Preparation of catalysts method is with embodiment 12, propene polymerizing method is with embodiment 11, just in catalyst preparation process, use dicyclo [2,2,1] hexyl-5-alkene-2, (ACROS reagent company provides 3-dioctyl phthalate methyl esters, preparation is referring to JP2004204097A) replace 9,10-dihydroanthracene-9,10-α, β-diethyl succinate.Test-results is as shown in table 1.
Embodiment 14
The preparation of Primary Catalysts: remove the internal electron donor compound and adopt 9,10-dihydroanthracene-9,10-α, outside β-diisopropyl ester amber acid, all the other are with embodiment 10.The content of each component is in the catalyzer: titanium 2.91%, electron donor compound 12.06%, magnesium 14.03%, chlorine 49.55%.
Slurry polymerization is with embodiment 10.
The polymerization relevant data is listed in table 1.
Embodiment 15
The preparation of Primary Catalysts is with embodiment 14.Slurry polymerization is with embodiment 11.
The polymerization relevant data is listed in table 1.
Embodiment 16
The preparation of Primary Catalysts: remove the internal electron donor compound and adopt 9,10-dihydroanthracene-9,10-α, outside β-Succinic Acid diisobutyl ester, all the other are with embodiment 10.The content of each component is in the catalyzer: titanium 2.58%, electron donor compound 9.61%, magnesium 13.66%, chlorine 47.46%.
Slurry polymerization is with embodiment 10.
The polymerization relevant data is listed in table 1.
Embodiment 17
The preparation of Primary Catalysts is with embodiment 16.Slurry polymerization is with embodiment 11.
The polymerization relevant data is listed in table 1.
Embodiment 18
Preparation of catalysts method and propene polymerizing method are just used 1-methyl-9 with embodiment 10 in catalyst preparation process, 10-dihydroanthracene-9, and 10-α, β-diisopropyl ester amber acid replaces 9,10-dihydroanthracene-9,10-α, β-dimethyl succinate.Test-results is as shown in table 1.
Embodiment 19
Preparation of catalysts method and propene polymerizing method are just used 2-methyl-9 with embodiment 10 in catalyst preparation process, 10-dihydroanthracene-9, and 10-α, β-diethyl succinate replaces 9,10-dihydroanthracene-9,10-α, β-dimethyl succinate.Test-results is as shown in table 1.
Embodiment 20
Preparation of catalysts method and propene polymerizing method are just used 2-tertiary butyl-9 with embodiment 10 in catalyst preparation process, 10-dihydroanthracene-9, and 10-α, β-Succinic Acid diisobutyl ester replaces 9,10-dihydroanthracene-9,10-α, β-dimethyl succinate.Test-results is as shown in table 1.
Embodiment 21
Preparation of catalysts method and propene polymerizing method are just used 1-chloro-9 with embodiment 10 in catalyst preparation process, 10-dihydroanthracene-9, and 10-α, β-Succinic Acid diisobutyl ester replaces 9,10-dihydroanthracene-9,10-α, β-dimethyl succinate.Test-results is as shown in table 1.
Embodiment 22
Preparation of catalysts method and propene polymerizing method are just used 2-chloro-9 with embodiment 10 in catalyst preparation process, 10-dihydroanthracene-9, and 10-α, β-Succinic Acid two cyclohexyls replace 9,10-dihydroanthracene-9,10-α, β-dimethyl succinate.Test-results is as shown in table 1.
The polymerizing condition of each embodiment of table 1 and experimental result
Claims (13)
1. load type main catalyst for propylene polymerization mainly is made up of spherical magnesium halide alcohol adduct, halogenated titanium, electron donor compound, it is characterized in that the electron donor compound has following structure:
Substituent R in the formula
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Identical 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 in the formula
9, R
10Identical or different, be selected from C
1～C
20Straight or branched alkyl, C
3～C
20Cycloalkyl, C
6～C
20Aryl or C
7～C
20Aralkyl; Each composition weight of Primary Catalysts consists of:
Electron donor compound 1-10%
Titanium 1-15%
Magnesium 10-25%
Halogen 40-60%.
2. Primary Catalysts according to claim 1, it is characterized in that the electron donor compound synthetic be that the mol ratio of anthracene or derivatives thereof and maleic anhydride is 1: (1～2) with anthracene or derivatives thereof and maleic anhydride reflux 1～8 hour in organic solvent; Be cooled to room temperature, slowly separate out crystallization, filtration, drying; Get solid chemical compound in alcoholic solvent, add p-methyl benzenesulfonic acid, the mol ratio of anthracene and p-methyl benzenesulfonic acid is 100: (1～50); Reflux 24～100 hours; Except that after desolvating, obtain after washing, extraction, the drying.
3. Primary Catalysts according to claim 2, it is characterized in that the electron donor compound synthetic be that the mol ratio of anthracene or derivatives thereof and maleic anhydride is 1: (1.1～1.5) with anthracene or derivatives thereof and maleic anhydride reflux 2～6 hours in organic solvent; Be cooled to room temperature, place and slowly separate out crystallization, filtration, drying; Get solid chemical compound in alcoholic solvent, add p-methyl benzenesulfonic acid, the mol ratio of anthracene and p-methyl benzenesulfonic acid is 100: (1～10); Reflux 48～90 hours; Except that after desolvating, obtain after washing, extraction, the drying.
4. Primary Catalysts according to claim 3 is characterized in that the electron donor compound is selected from following arbitrary compound:
9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
9,10-dihydroanthracene-9,10-α, β-diethyl succinate
9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
1-methyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
1-methyl-9,10-dihydroanthracene-9,10-α, β-diethyl succinate
1-methyl-9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
1-methyl-9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
1-methyl-9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
1-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
1-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
1-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
1-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
2-methyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
2-methyl-9,10-dihydroanthracene-9,10-α, β-diethyl succinate
2-methyl-9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
2-methyl-9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
2-methyl-9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
2-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
2-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
2-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
2-methyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
2-ethyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
2-ethyl-9,10-dihydroanthracene-9,10-α, β-diethyl succinate
2-ethyl-9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
2-ethyl-9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
2-ethyl-9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
2-ethyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
2-ethyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
2-ethyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
2-ethyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-diethyl succinate
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
2-tertiary butyl-9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
1-chloro-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
1-chloro-9,10-dihydroanthracene-9,10-α, β-diethyl succinate
1-chloro-9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
1-chloro-9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
1-chloro-9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
1-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
1-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
1-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
1-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
2-chloro-9,10-dihydroanthracene-9,10-α, β-dimethyl succinate
2-chloro-9,10-dihydroanthracene-9,10-α, β-diethyl succinate
2-chloro-9,10-dihydroanthracene-9,10-α, β-dipropyl succinate
2-chloro-9,10-dihydroanthracene-9,10-α, β-diisopropyl ester amber acid
2-chloro-9,10-dihydroanthracene-9,10-α, β-dibutyl succinate
2-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid diisobutyl ester
2-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two ring pentyl esters
2-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid two cyclohexyls
2-chloro-9,10-dihydroanthracene-9,10-α, β-Succinic Acid dibenzyl ester
5. Primary Catalysts according to claim 1 is characterized in that described magnesium halide alcohol adduct general formula is Mg (OR ')
mX
(2-m)N (R
2OH), 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.
6. Primary Catalysts according to claim 5 is characterized in that size-grade distribution 50～250 μ m of described magnesium halide alcohol adduct.
7. Primary Catalysts according to claim 6 is characterized in that magnesium halide in the described magnesium halide alcohol adduct is selected from a kind of in magnesium chloride, magnesium bromide, chloro magnesium methylate or the chloro magnesium ethylate; Alcohol is selected from a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols or the isopropylcarbinol.
8. Primary Catalysts according to claim 7 is characterized in that the magnesium halide in the described magnesium halide alcohol adduct is a magnesium chloride, and alcohol is ethanol.
9. Primary Catalysts according to claim 1 is characterized in that the halogenated titanium general formula is Ti (OR)
nX
(4-n), R is C in the formula
1-C
20Alkyl, aryl or aralkyl; X is a halogen; N is the integer of 0≤n＜4.
10. Primary Catalysts according to claim 9 is characterized in that halogenated titanium is selected from 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.
11. Primary Catalysts according to claim 10 is characterized in that halogenated titanium is a titanium tetrachloride.
12. method for preparing one of the described Primary Catalysts of claim 1 to 11, it is characterized in that the synthetic of Primary Catalysts is by after spherical magnesium halide alcohol adduct and the halogenated titanium reaction, obtain with the electron donor compound effects again, concrete steps are: 1) spherical magnesium halide alcohol adduct particle is joined in-50～20 ℃ the halogenated titanium liquid, reacted 1～6 hour, the mol ratio of magnesium and titanium is 1: 5～1: 100; 2) add the electron donor compound after being warming up to 30～80 ℃; 3) be warming up to 100～140 ℃ again, reacted 1～6 hour, the mol ratio of magnesium and electron donor compound is 2: 1～20: 1; 4) add halogenated titanium liquid with step (1) same amount after filtering again, in 100～140 ℃ of reactions 1～4 hour, more after filtration, obtain Primary Catalysts after the washing, drying.
13. according to the preparation method of the described Primary Catalysts of claim 12, it is characterized in that concrete steps are: 1) spherical magnesium halide alcohol adduct particle is joined in-30～0 ℃ the halogenated titanium liquid, reacted 1～4 hour, the mol ratio of magnesium and titanium is 1: 10～1: 50; 2) add the electron donor compound after being warming up to 40～60 ℃; 3) be warming up to 110～130 ℃ again, reacted 1～4 hour, the mol ratio of magnesium and electron donor compound is 2: 1～12: 1; 4) add halogenated titanium liquid with step (1) same amount after filtering again, in 100～140 ℃ of reactions 1～4 hour, more after filtration, obtain Primary Catalysts after the washing, drying.
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| EP2194070A1 (en) | 2008-12-03 | 2010-06-09 | Süd-Chemie Ag | Electron donor composition for a solid catalyst, solid catalyst composition used in the polymerisation of alpha-olefins, and process for the production of a polymer consisting of alpha-olefin units using the solid catalyst composition |
| CN102286118A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Titanium-containing solid catalyst component and catalyst for polymerization of olefin |
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| CN101759817B (en) * | 2008-12-03 | 2013-08-21 | Sc知识产权有限两合公司 | Electron donor composition for a solid catalyst, solid catalyst composition used in the polymerisation of alpha-olefins, and process for the production of a polymer |
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