CN1463990A - Process for preparing olefin polymerization ball type catalytic component and carrier - Google Patents
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Abstract
The spherical catalyst carrier is prepared with alcoholated magnesium chloride containing double-ether compound in emulsifying pelletizer. Liquid titanium halide compound is carried onto the spherical catalyst carrier to form spherical solid catalyst component in the presence of electron donor. In the X-ray diffraction spectrogram, the spherical solid catalyst component has diffraction peak in 13.3 deg of 2theta angle, strongest diffraction peak in 26.5 deg of 2theta angle and no characteristic diffraction peak of alpha-anhydrous MgCl2 in 15 deg of 2theta angle. The catalyst of the present invention has very high activity and may be used to produce polymer with good form, high apparent density and less fine powder. The catalyst is used in homopolymerization and copolymerization of olefin and suitable for various polymerization process.
Description
Technical field
The present invention relates to a kind of olefinic polymerization and copolymerization ball shape catalyst, mainly comprise the preparation method of ball-type carrier and ball-type ingredient of solid catalyst.Ball shape catalyst of the present invention is applicable to that propylene homopolymerization and alpha-olefin copolymer close.
Background technology
Olefin polymerization ball type catalytic came out for four more than ten years.U.S. Pat P3953414, USP411835 etc. have reported and have utilized magnesium chloride hydrate MgCl
26H
2O, spraying spheroiding carrier dewaters and forms MgCl under molten state
22H
2O, and then carry the titanium processing, obtain the ball-type ingredient of solid catalyst.The characteristics of this class catalyzer are that the polymkeric substance degree of isotacticity of catalyst activity and generation is low.Replace hydrate as the preparation support material with the magnesium chloride alcohol adduct, improved catalyst performance significantly.
The carrier prilling process mainly contains following several, injection, spray method, high-speed mixing method etc.English Patent GB2029480, Japanese Patent JP55155102-3, it is that the magnesium chloride alcohol adduct that reaction generates is spurted in the heat-eliminating medium through the long tube of 1mm diameter under pressure that European patent EP 029149A2, EP0243327A etc. have disclosed injection, forms the ball-type carrier, carrying titanium again handles, make the ball-type ingredient of solid catalyst, the shortcoming of this method is that spray tube is easily stifled, and particle is inhomogeneous, easily broken, the ball-type degree is relatively poor.Spray method be magnesium chloride alcohol adduct that magnesium chloride and ethanol synthesis are generated by spraying drying, or spray cooling equipment makes the ball-type carrier and carries titanium again and handle, must the ball-type ingredient of solid catalyst.This method equipment is complicated, generates the thinner carrier of particle, and it is reported that this catalyzer is used for propylene polymerization, and the polymkeric substance degree of isotacticity is lower.Japanese Patent JP55-135102, U.S. Pat P4,399,054, Chinese patent CN1047302A etc. has used high-speed mixing method that carrier is carried out granulation.High-speed mixing method is alcohol adduct and its not miscible inert dispersion medium that magnesium chloride and alcohol reaction are generated, high-speed stirring under temperature of reaction, dispersion medium is cut apart encirclement with the magnesium chloride alcohol adduct, forms independently alcohol adduct and melts and drip, and forms ball type carrier behind the chilling.Particularly Chinese patent CN1047302A describes the high-speed mixing method of preparation olefin polymerization ball type catalytic component in detail.The structure of its ball-type ingredient of solid catalyst is waited to levy for its X-ray diffraction spectrogram (Cuka) is that 2 θ angles are 35 ° and 14.95 ° and locate to occur diffraction peak or be 35 ° to no longer include reflection peak and replaced by the maximum intensity reflection peak that halogen is occurred between 2 θ angles are by 33.5 ° to 35 ° at 2 θ angles, is 14.95 ° at 2 θ angles and locates not occur reflection peak.Its catalyst performance is better, and the polymkeric substance of generation is (d=1-5mm) spherical granules, but the pure content of the ball-type carrier of its preparation is higher, so must dealcoholysis before carrying titanium.Because alcohol adduct and TiCl
4Speed of response is very fast, and emits with a large amount of heats, must in time withdraw from, otherwise produce local superheating, causes the carrier granule fragmentation.
Summary of the invention
Advantages such as the object of the present invention is to provide a kind of olefin polymerization ball type catalytic, this catalyst component and promotor polymerization be olefin polymerization together, and the polymer yield height and the polymkeric substance of generation have the apparent density height, and form is good, and fine powder is few.
Another purpose of the present invention is to provide the method for the above-mentioned catalyzer of preparation, and its operational condition gentleness of this method can be used present conventional equipment
For achieving the above object, olefin polymerization ball type catalytic component provided by the invention
The bis ether compound that the present invention is used to prepare the ball-type carrier is mainly and condenses polyacetylene compound, as indene derivative, fluorene derivatives, naphthalene derivatives, phenanthrene derivative and anthracene derivant etc., example has: 1, two (methoxymethyl) indenes, 1 of 1-, two (methoxymethyl)-2 of 1-, 3-dimethyl indenes, 1, two (methoxymethyl)-3 of 1-, 6-dimethyl indenes, 1, two (the methoxymethyl)-7-methyl indenes, 1 of 1-, two (the methoxymethyl)-4-phenylindan, 1 of 1-, two (the methoxymethyl)-cyclopentyl indenes, 1 of 1-, two (the methoxymethyl)-cyclohexyl indenes of 1-etc.9, two (methoxymethyl) fluorenes of 9-, 9, two (the methoxymethyl)-2-methyl fluorenes of 9-, 9, two (the methoxymethyl)-2-propyl group fluorenes of 9-, 9, two (the methoxymethyl)-2-isobutyl-fluorenes of 9-, 9, two (the methoxymethyl)-2-butyl fluorenes of 9-, 9, two (methoxymethyl)-2 of 9-, 7-dipropyl fluorenes, 9, two (methoxymethyl)-2 of 9-, 7-dibutyl fluorenes, 9, two (methoxymethyl)-2,3 of 9-, 6,7-tetraethyl-fluorenes, 9, two (methoxymethyl)-1 of 9-, 4-methane dihydronaphthalene, 9, two (methoxymethyl)-9 of 9-, the 10-dihydroanthracene, 1, two (methoxymethyl)-1 of 1-, 2-dihydronaphthalene, 4, two (the methoxymethyl)-1-phenyl-3 of 4-, the 4-dihydronaphthalene, 4, two (the methoxymethyl)-1-phenyl-1 of 4-, 4-dihydronaphthalene etc.
When the present invention contains the magnesium chloride alcohol adduct ball-type carrier of bis ether compound in preparation, the bis ether compound at alcohol fashionable or (with) when carrying titanium, add.Generate the ball-type vehicle group and become MgCl
2NROHm (bis ether compound), R=2.4-3.3 in the formula, m=0.01-0.40.
When the present invention contained the magnesium chloride alcohol adduct of bis ether in preparation, used magnesium chloride was a Magnesium Chloride Anhydrous, and its water content is less than 1.5%, and particle diameter is 125-450 μ m.When the present invention contained the magnesium chloride alcohol adduct of bis ether compound in preparation, used monohydroxy-alcohol was C
1-C
8Straight chain and branched-chain alcoho, for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, octanol and isooctyl alcohol etc.Be preferably C
2-C
4Straight chain alcohol, ethanol preferably.Alcohol is 2.8-3.6 with the mol ratio of magnesium.
Solvent for use was vaseline oil, white oil and whiteruss when the present invention contained the magnesium chloride alcohol adduct of bis ether compound in preparation, and the present invention selects white oil (viscosity 14mm for use
2/ s).
When the present invention contained the magnesium chloride alcohol adduct ball-type carrier of bis ether compound in preparation, used dispersion medium was white oil and methyl-silicone oil (320-370mm
2/ s).
When the present invention contained the magnesium chloride alcohol adduct ball-type carrier of bis ether compound in preparation, used heat-eliminating medium can be used hexane, heptane, kerosene etc., and the present invention selects hexane for use.
The present invention prepares the used liquid titanium halogen compound of ball-type ingredient of solid catalyst, and its general formula is Ti (OR)
nX
4-n, R is C in the formula
1-C
18Alkyl, X are halogen atom, and 0≤n≤4 mainly comprise following several liquid titanium halogen compound:
Titanium tetrahalide: TiCl
4, TiBr
4Deng.
Three halogenated alkoxy titaniums: Ti (OCH
3) Cl
3, Ti (OC
2H
5) Cl
3, Ti (OC
2H
5) Br
3
Dihalo dialkoxy titanium: Ti (OCH
3)
2Cl
2, Ti (OC
2H
5)
2Cl
2, Ti (OC
2H
5)
2Br
2
One halo, three alcoxyl clump partners: Ti (OCH
3)
3Cl, Ti (OC
2H
5)
3Cl, Ti (OC
2H
5)
3Br.
Titanic acid ester: Ti (OC
2H
5)
4, Ti (OC
4H
9)
4
The present invention preferably titaniferous compound of usefulness is TiCl
4
The present invention when preparation ball-type ingredient of solid catalyst, TiCl
4The mol ratio of consumption Ti/Mg is 20-80,30-60 preferably, and the contact temperature is-10 to-25 ℃.
The present invention is when preparation ball-type ingredient of solid catalyst, and used electron donor compound comprises mainly and contain oxygen and nitrogenous compound that wherein organic acid acetic is preferred.They comprise saturated and unsaturated aliphatic carboxylicesters, alicyclic carboxylic ether and aromatic carboxylic acid esters.Example has: methyl acetate, ethyl acetate, butylacetate, methyl propionate, ethyl propionate, butyl propionate, methyl-butyrate, ethyl butyrate, Valeric acid ethylester, ethyl benzoate, propyl benzoate, butyl benzoate, ethyl anisate, dimethyl succinate, diethyl succinate, diethyl malonate, butyl ethyl malonate, dimethyl maleate, ethyl maleate, dibutyl maleinate, the phthalic acid mono ethyl ester, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, n-butyl phthalate, diisobutyl phthalate, dioctyl phthalate (DOP), dimixo-octyl phthalate etc.Ethyl benzoate preferably.
Olefinic polymerization of the present invention and copolymerization ball shape catalyst by (A), (B) and (C) three components form:
(A) be ball-type ingredient of solid catalyst of the present invention.
(B) be promotor, be mainly alkylaluminium cpd, as triethyl aluminum, triisobutyl aluminium etc.When polymerization, use the Al/Ti mol ratio to be 30-2000, preferably 500-1400.
Olefin polymerization catalysis of the present invention generally need not add the exoelectron donor when the alkene tactic polymerization.But for special requirement also can add exoelectron donor (C) usually, be mainly silicoorganic compound, its general formula is R
1R
2Si (OR)
n, R contains C in the formula
1-C
4Alkyl, R
1And R
2Can be alkyl, cycloalkyl or aryl identical and inequality.Example has: dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl diethoxy silane, dipropyl dimethoxy silane, dipropyl diethoxy silane, dibutyl dimethoxy silane, dibutyl diethoxy silane, methylcyclohexyl dimethoxy silane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, dicyclohexyl dimethoxy silane, dicyclohexyl diethoxy silane, dimethoxydiphenylsilane etc.Dicyclopentyl dimethoxyl silane preferably.
The preparation method who contains the magnesium chloride alcohol adduct ball-type carrier of bis ether compound
Under nitrogen protection, Magnesium Chloride Anhydrous and monohydroxy-alcohol are pressed feed ratio ROH/MgCl
2=2.8-3.6 (mol ratio), and an amount of bis ether compound and white oil be added in the reactor, in 110-130 ℃ of reaction 1-3 hour, forms homogeneous solution.Adding is given and is heated to 110-130 ℃ earlier then, and volume ratio is 1: the silicone oil of 1-15 and white oil, and the revolution with 500-800 rev/min stirred 10-60 minute under this temperature.Under the nitrogen effect, while stirring with material in the reactor in mulser is transported to-25 to-35 ℃ heat-eliminating medium.The ball-type carrier suspended substance outlet temperature that generates is 0 ℃ ± 3 ℃.Filter the ball-type carrier that generates, and with hexane wash for several times, obtain containing the ball-type carrier of bis ether compound through vacuum-drying.Its chemical constitution is: MgCl
2NROHm (bis ether compound), n=2.4-3.3 in the formula, m=0.01-0.40.Ball-type carrier of the present invention is that the mulser by the various models of domestic and imported makes.
Ball-type ingredient of solid catalyst preparation method:
Under nitrogen protection, the magnesium chloride alcohol adduct ball-type carrier that contains the bis ether compound of above-mentioned preparation joined in the reactor be cooled to-10 to-25 ℃ gradually, add the TiCl that is cooled to-10 to-25 ℃ in advance then
4, its add-on is Ti/Mg=30-60 (mol ratio).Slowly heat up then, at 60 ℃ of adding electron donors.Temperature is elevated to 100-130 ℃ again, reacted 2-3 hour, after the liquid-solid separation, in solid product, add a certain amount of TiCl again
4When temperature arrives 60 ℃, add electron donor, and temperature is continued to be elevated to 100-130 ℃, reacted 1-2 hour.Reaction finishes back separate solid product and washes for several times with industrial hexane.Get the ball-type ingredient of solid catalyst through vacuum-drying, its chemical constitution is Ti 2.0-4.0%, Mg 13.0-20.0%, Cl 40.0-60.0%, electron donor 1.0-8.0%, 9, two (methoxymethyl) fluorenes 5.0-20.0% of 9-.
Embodiment
Further specify method of the present invention with example below, but the invention is not restricted to this.
Embodiment 1
Contain 9, the preparation of the ball-type carrier of two (methoxymethyl) fluorenes of 9-
Under nitrogen protection, with 95.2 gram Magnesium Chloride Anhydrouss, 190.40 milliliters of dehydrated alcohols (alcohol/magnesium mol ratio is 3.24) and 240 milliliters of white oils are added in the reactor.Heat up 127 ℃, be stirred to MgCl
2All the dissolving back adds 179.4 mmoles 9, and two (methoxymethyl) fluorenes of 9-continue to stir 2 hours, and stopped reaction obtains containing 9, the magnesium chloride alcohol adduct homogeneous solution of two (methoxymethyl) fluorenes of 9-.
Foretell in nitrogen protection, 1000 milliliters and the 100 milliliters silicone oil of white oil that are heated to 127 ℃ in advance are added in the reactor and contain 9, the magnesium chloride alcohol adduct homogeneous solution of two (methoxymethyl) fluorenes of 9-mixes, and with 500-800 rev/min revolution stirring 30 minutes.Under the nitrogen pressure effect, material is transported in advance through mulser in 5 liters of (stirring) hexanes that are cooled to-25 to-35 ℃ in the reactor then.The ball-type carrier suspended substance of heat-eliminating medium hexane and generation continues to stir, and its outlet temperature is 0 ℃ ± 3 ℃.Continue to stir, when temperature reaches 10-20 ℃, stop to stir.Separate the ball-type carrier, it is dry that ball-type carrier 247 restrains to clean final vacuum with hexane, and ball-type carrier chemical constitution is MgCl
22.8C
2H
5OH0.1581[9, two (methoxymethyl) fluorenes of 9-], granularity 30-130 μ m.Claim that this carrier is carrier (A).
By the condition of above-mentioned preparation ball-type carrier, but add 9, the mmole of two (methoxymethyl) fluorenes of 9-is counted difference, and the carrier that obtains is respectively carrier (B), carrier (C) and carrier (D), sees table 1 for details.Table 1
(B) (C) (D) for container name (A)
Bis ether add-on (mmol) 179.4 183.9 152.0 0
MgCl
2/ bis ether (mol ratio) 5.57 5.44 6.58 0
The preparation of solid ball type catalytic component:
Under nitrogen protection, 5 gram carriers (A) are joined in the reactor and with it and are cooled to-20 ℃, will be cooled to 125 milliliters of TiCl of-20 ℃ then in advance
4Be added in the reactor, slowly be warming up to 60 ℃, add ethyl benzoate 5.6 mmoles and be warming up to 110 ℃ of maintenances 2 hours, add 125 milliliters of TiCl after the filtration again
4Elevated temperature also adds ethyl benzoate 2.5 mmoles for the second time in the time of 60 ℃, continue to be warmed up to 110 ℃ of reaction liquid-solid separation after 1 hour, adds 125 milliliters of TiCl again
4, 110 ℃ of insulations 1 hour, filtering, solid part washs 5 times at 60 ℃ with industrial hexane, each 100 milliliters of hexanes, vacuum-drying gets the ball-type ingredient of solid catalyst.
The X-ray diffraction spectrogram of ball-type ingredient of solid catalyst:
The X-ray diffraction spectrogram is 15 ° at 2 θ angles and locates not occur the strong diffractive features peak of α-Magnesium Chloride Anhydrous, locates to occur diffraction peak and be 13.5 ° at 2 θ angles, and at 2 θ angles is 26.5 ° and locates to occur the strongest diffraction peak.
The chemical constitution of ball-type ingredient of solid catalyst: Ti 2.48%, Mg 14.76%, and Cl 51.50%, 9, two (methoxymethyl) fluorenes 11.50% of 9-, ethyl benzoate 4.14%.
Propylene polymerization
Three liters of autoclaves are used N under 100 ℃
2Pump drainage repeatedly, with propylene gas displacement postcooling to 30 ℃ and under propylene atmosphere, add AlEt
30.6 milliliter, 6 milligrams of ingredients of solid catalyst, 2 liters of liquid propenes and hydrogenation 0.2MPa.Be warming up to 70 ℃ then, polymerization under agitation 2 hours gets ball-type polypropylene 786 grams after the drying.Catalyst efficiency 131.0KgPP/gcat, apparent density 0.46g/cm
3, isotactic index 98.01%.
Embodiment 2-3
Use carrier (B) and carrier (C) preparation ball-type ingredient of solid catalyst, other condition is with embodiment 1, and polymerization result is listed table 2 in.
Table 2
| Embodiment number | Carrier | The ball-type ingredient of solid catalyst | Catalyst efficiency KgPP/gcat | Apparent density g/cm 3 | Isotactic index (%) | ||||
| Titanium (%) | Magnesium (%) | Chlorine (%) | Bis ether (%) | ?EB ?(％ | |||||
| ?1 | ?A | ?2.48 | ?14.76 | ?51.50 | ?11.50 | ?4.14 | ?131.0 | ?0.46 | ?98.01 |
| ?2 | ?B | ?2.96 | ?14.76 | ?51.80 | ?11.38 | ?4.37 | ?123.0 | ?0.45 | ?97.83 |
| ?3 | ?C | ?2.88 | ?14.21 | ?50.59 | ?11.17 | ?3.88 | ?116.0 | ?0.47 | ?97.61 |
EB is an ethyl benzoate; Bis ether is 9,9-(methoxymethyl) fluorenes.
Embodiment 4-6
Change the add-on of ethyl benzoate, other conditions are with embodiment 1, and its result lists table 3 in.
Table 3
| Embodiment number | Carrier | Carry titanium and add the EB amount | The ball-type ingredient of solid catalyst | Catalyst efficiency KgPP/gcat | Apparent density g/cm 3 | Isotactic index (%) | |||||
| The 1st mol | The 2nd mol | Titanium (%) | Magnesium (%) | Chlorine (%) | Bis ether (%) | ?EB ?(％) | |||||
| 4 | ?A | ?5.6 | ?6.4 | ?3.38 | ?14.46 | ?52.10 | ?11.88 | ?5.28 | ?121.0 | ?0.44 | ?97.48 |
| 5 | ?A | ?3.2 | ?2.5 | ?2.57 | ?14.21 | ?50.59 | ?10.28 | ?3.07 | ?101.3 | ?0.44 | ?97.26 |
| 6 | ?A | ?5.6 | ?0.0 | ?3.20 | ?14.26 | ?51.68 | ?11.31 | ?2.14 | ?108.6 | ?0.44 | ?97.35 |
EB is an ethyl benzoate; Bis ether is 9,9-(methoxymethyl) fluorenes.
Embodiment 7-9
Press the step of embodiment 1, just change ethyl benzoate into n-butyl phthalate, diisobutyl phthalate and dioctyl phthalate (DOP), its polymerization result is listed table 4 in.
Table 4
| Embodiment number | Carrier | The ball-type ingredient of solid catalyst | Catalyst efficiency KgPP/gcat | Apparent density g/cm 3 | Isotactic index (%) | ||||
| Titanium (%) | Magnesium (%) | Chlorine (%) | Bis ether (%) | ?D ?(％) | |||||
| 7 | ?A | ?2.36 | ?15.10 | ?57.64 | ?12.25 | ?3.25 | ?59.3 | ?0.45 | ?97.15 |
| 8 | ?A | ?2.87 | ?12.95 | ?56.28 | ?11.55 | ?3.58 | ?77.0 | ?0.45 | ?97.35 |
| 9 | ?A | ?2.65 | ?16.39 | ?55.65 | ?10.50 | ?4.05 | ?67.0 | ?0.44 | ?98.58 |
D is a Bisphthalate; Bis ether is 9,9-(methoxymethyl) fluorenes
Embodiment 10
The preparation of ball-type ingredient of solid catalyst:
Under nitrogen protection, 5 gram carriers (A) are joined in the reactor and with it and are cooled to-20 ℃, will be cooled to 62.5 milliliters of TiCl of-20 ℃ then in advance
4Be added in the reactor with 62.5 milliliters of toluene mixture, slowly be warming up to 60 ℃, add ethyl benzoate 5.6 mmoles, continue elevated temperature to 110 ℃, reacted 2 hours.Again add 62.5 milliliters of TiCl after the liquid-solid separation
4With 62.5 milliliters of toluene mixture, be warming up to 60 ℃, add ethyl benzoate 2.5 mmoles, continue to be warming up to 110 ℃, reacted 1 hour.Again add TiCl after the filtration
4125 milliliters.110 ℃ of reactions 1 hour, filter, with industrial hexane wash 5 times, 100 milliliters/time.Vacuum-drying gets the ball-type ingredient of solid catalyst, and it consists of: Ti 2.88%, and Mg 16.48%, and Cl 58.26%, ethyl benzoate 4.28%, 9, two (methoxymethyl) fluorenes 11.22% of 9-.
It is as follows to press embodiment 1 method polymerization result: catalyst efficiency 98.0kgPP/gcat, polymkeric substance apparent density 0.41g/cm
3, isotactic index 97.72%.
Comparative example 1
The preparation of ball-type ingredient of solid catalyst:
Under nitrogen protection, 5 gram carriers (D) are joined in the reactor and with it and are cooled to-20 ℃, will be cooled to 125 milliliters of TiCl of-20 ℃ then in advance
4Be added in the reactor, be warming up to 60 ℃ in 1.5 hours, add ethyl benzoate 5.6 mmoles, continue elevated temperature to 70 ℃, add 2.5 mmoles 9, two (methoxymethyl) fluorenes of 9-rise to 110 ℃ with temperature, react 2 hours.Again add 125 milliliters of TiCl after the liquid-solid separation
4, be warming up to 60 ℃, add ethyl benzoate 2.5 mmoles, continue to be warming up to 70 ℃ and add 1.3 mmoles 9, two (methoxymethyl) fluorenes of 9-rise to 110 ℃ of reactions 1 hour with temperature.Again add 125 milliliters of TiCl after the filtration
4, 110 ℃ of insulations 1 hour, filter, with industrial hexane wash 5 times, each 100 milliliters.Vacuum-drying gets the ball-type ingredient of solid catalyst.The chemical constitution of ball-type ingredient of solid catalyst: Ti 3.17%, Mg 14.26%, and Cl 52.48%, 9, two (methoxymethyl) fluorenes 11.76% of 9-, ethyl benzoate 4.28%.
Propylene polymerization
Polymerizing condition is with embodiment 1, and polymerization result is as follows: catalyst efficiency 114.0KgPP/gcat, the apparent density 0.44g/cm of polymkeric substance
3, isotactic index 97.36%.
Embodiment 11
It is as follows to carry out second third copolymerization process by the ball-type ingredient of solid catalyst of embodiment 1 preparation:
Three liters of autoclaves are used N under 100 ℃
2The gas pump drainage repeatedly, with propylene gas displacement postcooling to 30 ℃ and under propylene atmosphere, add AlEt
30.72 milliliter, 7.2 milligrams of ingredients of solid catalyst, 2 liters of liquid propenes, hydrogenation 0.2Mpa and 0.4Mpa ethene.Be warming up to 70 ℃ then, polymerization under agitation 2 hours gets ball-type b-propylene copolymer 626 grams after the drying.Catalyst efficiency 87.0KgPP/gcat, apparent density 0.43g/cm
3, isotactic index 88.65%, melting index 12.73g/10min, 153.06 ℃ of fusing points.
Embodiment 12
It is as follows to carry out slurry polymerisation process of ethylene by the ball-type ingredient of solid catalyst of embodiment 1 preparation:
Two liters of autoclaves are used N under 100 ℃
2The gas pump drainage repeatedly, with ethylene gas displacement postcooling to 30 ℃ and under ethene atmosphere, add 1 liter of refined hexane and 0.89ml (0.0065 mole) triethyl aluminum, and the ball-type ingredient of solid catalyst 15mg of adding embodiment 1 preparation (0.0000217 mole is pressed titanium and calculates).Then, being warming up to 70 ℃ of adding dividing potential drops is the hydrogen of 0.2Mpa, continues to be warming up to 80 ℃, feeds ethene to still pressure and is 0.8Mpa.Polyreaction is 2 hours under this temperature, and pressure remains on 0.8Mpa in the reaction process.Reaction is closed intake valve after finishing, and logical water coolant to room temperature, stops the still temperature drop to stir, and gets rid of unreacting gas, obtains reaction product, gets 128 gram white polymer through vacuum-drying.Catalyst efficiency 8.53kgPP/gcat, tap density 0.32g/cm
3, 137.27 ℃ of fusing points.
Claims (8)
1, a kind of olefin polymerization ball type ingredient of solid catalyst, its chemical constitution is: Ti 2.0-4.0%, Mg 13.0-20.0%, Cl 40.0-60.0%, electron donor 1.0-8.0%, 9, two (methoxymethyl) fluorenes 5.0-20.0% of 9-; Be 13.3 ° at 2 θ angles and locate to occur diffraction peak, and at 2 θ angles be 26.5 ° and locate to occur the strongest diffraction peak.
2, catalyst component as claimed in claim 1 is characterized in that, described electron donor is saturated and unsaturated aliphatic carboxylicesters, alicyclic carboxylic ether or aromatic carboxylic acid esters.
3, a kind of preparation method of olefin polymerization ball type ingredient of solid catalyst carrier, its key step is: under nitrogen protection, Magnesium Chloride Anhydrous and monohydroxy-alcohol are pressed feed ratio ROH/MgCl
2=2.8-3.6 (mol ratio), and bis ether compound and white oil be added in the reactor, in 110-130 ℃ of reaction 1-3 hour, forms homogeneous solution; Adding is given and is heated to 110-130 ℃ earlier then, and volume ratio is 1: the silicone oil of 1-15 and white oil, and the revolution with 500-800 rev/min stirred 10-60 minute under this temperature; Under the nitrogen effect, while stirring with material in the reactor through mulser is transported to-25 to-35 ℃ heat-eliminating medium with 1500-8000 rev/min in, the ball-type carrier suspended substance outlet temperature that generates is 0 ℃ ± 3 ℃, filter the ball-type carrier that generates, and for several times with hexane wash, obtain containing the ball-type carrier of bis ether compound through vacuum-drying, it consists of MgCl
2NROHm (bis ether compound), n=2.4-3.3 in the formula, m=0.01-0.40.
4, the preparation method of carrier as claimed in claim 3 is characterized in that, described monohydroxy-alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, isopropylcarbinol, amylalcohol, hexanol, octanol or/and isooctyl alcohol, preferred alcohol.
5, the preparation method of carrier as claimed in claim 3 is characterized in that, described bis ether compound is indene derivative, fluorene derivatives, naphthalene derivatives, phenanthrene derivative or anthracene derivant, and is preferred 9, two (methoxymethyl) fluorenes of 9-.
6, a kind of method for preparing the described catalyst component of claim 1, its key step is: under nitrogen protection, the ball-type carrier of the catalyst component of claim 3 preparation joined in the reactor be cooled to-10 to-25 ℃ gradually, add the liquid titanium halogen compound that is cooled to-10 to-25 ℃ in advance then, its add-on is Ti/Mg=30-60 (mol ratio), slowly heat up then, at 60 ℃ of adding electron donors; Temperature is elevated to 100-130 ℃ again, reacted 2-3 hour, after the liquid-solid separation, in solid product, add the liquid titanium halogen compound again; When temperature arrives 60 ℃, add electron donor, and temperature is continued to be elevated to 100-130 ℃, reacted 1-2 hour; Reaction finishes back separate solid product and washes for several times with industrial hexane, gets the ball-type ingredient of solid catalyst through vacuum-drying.
7, the preparation method of catalyst component as claimed in claim 6 is characterized in that, the general formula of described liquid titanium halogen compound is: TiX
n(OR)
4-n, R is C in the formula
1-C
18Alkyl, X are halogen, the n=1-4 mole.
As the preparation method of claim 6 or 7 described catalyst components, it is characterized in that 8, described liquid titanium halogen compound is preferably TiCl
4
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| WO2007112700A1 (en) | 2006-04-06 | 2007-10-11 | China Petroleum & Chemical Corporation | Magnesium halide adduct, olefins polymerization catalyst component and catalyst made therefrom |
| EP2287208A1 (en) | 2009-08-13 | 2011-02-23 | China Petroleum & Chemical Corporation | A catalyst component for olefin polymerization and a catalyst comprising the same |
| WO2011044761A1 (en) | 2009-10-16 | 2011-04-21 | 中国石油化工股份有限公司 | Carrier for olefin polymerization catalyst, preparation method and application thereof |
| WO2011047522A1 (en) | 2009-10-20 | 2011-04-28 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof |
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