CN102079796B - Load type olefin polymerization solid catalyst as well as preparation method and application of load type olefin polymerization solid catalyst - Google Patents
Load type olefin polymerization solid catalyst as well as preparation method and application of load type olefin polymerization solid catalyst Download PDFInfo
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- CN102079796B CN102079796B CN2009102241730A CN200910224173A CN102079796B CN 102079796 B CN102079796 B CN 102079796B CN 2009102241730 A CN2009102241730 A CN 2009102241730A CN 200910224173 A CN200910224173 A CN 200910224173A CN 102079796 B CN102079796 B CN 102079796B
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Abstract
The invention relates to a load type olefin polymerization solid catalyst which comprises a magnesium-containing carrier the general structure of which is ClMg(OR).n(ROH), wherein in pyridine-2-alkyl imine titanium tetrachloride and TiCl4 as shown in a formula I which is disclosed in the specification and the carrier ClMg(OR).n(ROH), R is selected from C1-C4 alkyl, and n is 0.1-1.0; and in the formula (I), R1 and R2 are respectively a mono-substituent group or a multi-substituent group on a pyridine ring and an aniline ring and are respectively selected from hydrogen, C1-C6 alkyl, phenyl or C7-C8aralkyl, R3 is selected from hydrogen or C1-C3 alkyl; and in the catalyst, the content of magnesium is 2-18wt%, the content of titanium is 1.0-9.0wt%, and the content of nitrogen is 0.1-2.0wt%. The catalyst is used in olefin polymerization reaction and has the characteristic of good hydrogen regulation sensitivity.
Description
Technical field
The present invention is a kind of load type olefin polymerization solid catalyst and preparation and uses, specifically, is a kind of with TiCl
4With titanium complex be olefin polymerization solid catalyst and the preparation method and the application of active ingredient.
Background technology
In the olefin polymetiation process process; Hydrogen is as the chain-transfer agent and the chain terminator of olefinic polymerization; Usually be used as the regulator of polyolefine relative molecular mass,, can regulate and control molecular weight of polymer through changing the hydrogen usage in the polymerization process; Therefore, the hydrogen regulation performance of olefin polymerization catalysis is an important indicator of catalyzer over-all properties.
In the course of processing of polyolefine material, the melting index of polymkeric substance is one of important indicator of investigating the polymer processing performance, and the size of melting index has embodied molecular weight of polymer and distribution thereof.Relative molecular mass and distribution thereof have very big influence to poly performance, and relative molecular mass is big, and melting index is low, its satisfactory mechanical property, but be difficult for processing; Relative molecular mass is little, and melting index is high, and processing characteristics is excellent, but mechanical property is relatively poor.Different relative molecular masses, just the polyolefine of different melting index has different Application Areass.In Industrial processes; Catalyzer with high hydrogen response ability can be easily through adjusting the melting index of hydrogen branch pressure-controlled product; Can produce the polyolefine of bimodal relative molecular mass distribution and the product of high fusion index, be particularly suitable for producing the food product pack and the family expenses object of each generic request thin-walled.
CN101117362A discloses a kind of magnesium-containing carrier, has the general expression of ClMg (OR) n (ROH), and R is selected from C in the general formula
1～C
5Alkyl, n is 0.1～1.0.The not activated direct load TiCl of this carrier
4Can make olefin polymerization solid catalyst, have advantages of high catalytic activity.
CN1580084A discloses a kind of dual-active property component polyolefin catalyst and preparation method, uses general formula to be MgCl
2The magnesium chloride alcohol adduct of n (ROH) is a carrier, load active component TiCl
4And pyridine-2-alkyl imines titanium tetrachloride makes solid catalyst, and this catalyzer has double activity center, can make the polymkeric substance of bimodal or wide molecular weight distribution, and resulting polymers has single HMP and high-crystallinity, and percent crystallinity is generally greater than 65%.
CN101205264A discloses a kind of ethane polymerization solid catalyst, and the carrier of this catalyzer is MgCl
2, active ingredient is TiCl
4, the internal electron donor compound is pyridine-2-alkyl imines, has narrower MWD by the Vilaterm of this Preparation of Catalyst, highly linear, and have excellent physical and mechanical properties.
Summary of the invention
The purpose of this invention is to provide a kind of supported olefin polymerization catalyst and preparation method, this catalyzer has high hydrogen response, under identical hydrogen ethylene partial pressure condition, can prepare and has the more polyolefin products of high fusion index.
Olefin polymerization catalysis provided by the invention comprises that general formula is the magnesium-containing carrier of ClMg (OR) n (ROH), the pyridine shown in the formula (I)-2-alkyl imines titanium tetrachloride and TiCl
4,
Among said support C lMg (OR) n (ROH), R is selected from C
1～C
4Alkyl, n is 0.1～1.0, in the formula (I), R
1, R
2Be respectively single substituting group or multi-substituent on pyridine ring and the aniline ring, be selected from hydrogen, C respectively
1～C
6Alkyl, phenyl or C
7～C
8Aralkyl, R
3Be selected from hydrogen or C
1～C
3Alkyl, Mg content is that 2～18 quality %, titanium content are that 1.0～9.0 quality %, nitrogen content are 0.1～2.0 quality % in the said catalyzer.
It is carrier that the present invention selects specific magnesium-containing compound, and pyridine imine and titanium tetrachloride are mixed with active component solution, the not activated direct load active component of carrier, and the solid catalyst that obtains is used for olefinic polyreaction, has higher hydrogen response.
Embodiment
The present invention is a carrier with magnesium-containing compound ClMg (OR) n (ROH), with pyridine-2-alkyl group with imine moiety and TiCl
4Hybrid reaction in unreactive hydrocarbons generates pyridine-2-alkyl imines titanium tetrachloride and TiCl by a certain percentage
4Mixing solutions, be the catalyst activity component solution.Described carrier is disperseed with stable hydrocarbon, the catalyst activity component solution is added in the dispersive carrier carry out active constituent loading again, the gained solids wash is drying to obtain catalyzer of the present invention.Catalyzer hydrogen response of the present invention is higher; When being used for olefinic polyreaction, compare, can under lower hydrogen partial pressure, obtain same melt exponential polyolefine with similar Ziggler-Natta catalyzer; Perhaps depress, obtain the higher polymeric articles of melting index at same hydrogen branch.
Said support C lMg (OR) n (ROH) generates magnesium-containing compound with low-carbon alcohol with the suitable proportion reaction by the magnesium powder in the presence of methyl chloride, with stable hydrocarbon the compound of generation is separated out, and is drying to obtain carrier again.In the carrier general formula, ROH is the alcohol with magnesium powder reaction, (OR) group from the alcohol of magnesium powder reaction in alkoxyl group, the preferred C of described R
2～C
4Alkyl, when n=0.5～1.0, carrier is a crystalline material, n was less than 0.5 o'clock, carrier is an amorphous substance.Described ROH preferred alcohol, propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
The active ingredient of solid catalyst of the present invention has two kinds, and a kind of is titanium tetrachloride, and another kind is the pyridine shown in the formula (I)-2-alkyl imines titanium tetrachloride.
In the formula (I), R
1, R
2Be respectively single substituting group or multi-substituent on pyridine ring and the aniline ring, R
1And R
2Preferred hydrogen of difference or C
1～C
4Alkyl, the substituent R on the pyridine ring
1Number can be 1～4, replace the position and be preferably 4 or 6 of pyridine ring.Substituent R on the phenyl ring
2Number be 1～5, preferred 1～3, replace the position and preferably be positioned at 2,4,6 of phenyl ring.R
1And R
2More preferably hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl.R
3Be the substituting group on the imines carbon atom, preferred hydrogen, methyl or ethyl.
Preferred 2～15 quality % of Mg content, preferred 2.0～7.0 quality % of titanium content, preferred 0.5～2.0 quality % of nitrogen content in the catalyzer of the present invention.
Preparation of catalysts method provided by the invention comprises the steps:
(1) preparation active component solution: pyridine-2-alkyl group with imine moiety is dissolved in the halogenated alkane, adds TiCl
4, said pyridine-2-alkyl group with imine moiety and TiCl
4Mol ratio be 1: 1.1～15,
(2) preparation catalyzer: ClMg (OR) n (ROH) is suspended in the unreactive hydrocarbons; The active component solution that adds the preparation of (1) step; Fully after the reaction with the gained solid with unreactive hydrocarbons washing, drying, said ClMg (OR) n (ROH) is 1: 10～100 with the mass ratio of unreactive hydrocarbons, with TiCl
4Mass ratio is 0.2～15.0: 1.
In the aforesaid method; (1) step is the preparation active component solution; Pyridine-2-alkyl group with imine moiety is dissolved with halogenated alkane; Add excessive titanium tetrachloride and fully react, titanium tetrachloride and pyridine-2-alkyl group with imine moiety reaction obtains pyridine-2-alkyl imines titanium tetrachloride, promptly contains TiCl in the reacted mixing solutions
4And pyridine-two kinds of active ingredients of 2-alkyl imines titanium tetrachloride.
Described pyridine-2-alkyl group with imine moiety has the described structure expression of formula (II):
In the formula (II), R
1～R
3Identical with the qualification in the formula (I).
Pyridine-2-alkyl group with imine moiety that the present invention uses is preferred: N-(2, the 6-3,5-dimethylphenyl)-2-pyridine azomethine, N-(2,6-diethylammonium phenyl)-2-pyridine azomethine; N-(2, the 6-diisopropyl phenyl)-2-pyridine azomethine, N-(2,6-diisobutyl phenyl)-2-pyridine azomethine; N-(2, the 6-di-tert-butyl-phenyl)-2-pyridine azomethine, N-(2,6-dibenzyl phenyl)-2-pyridine azomethine; N-(2, the 4-3,5-dimethylphenyl)-2-pyridine azomethine, N-(2,4-diethylammonium phenyl)-2-pyridine azomethine; N-(2, the 4-diisopropyl phenyl)-2-pyridine azomethine, N-(2,4-diisobutyl phenyl)-2-pyridine azomethine; N-(2, the 4-di-tert-butyl-phenyl)-2-pyridine azomethine, N-(2,4-dibenzyl phenyl)-2-pyridine azomethine;
N-(2-ethylphenyl)-2-pyridine azomethine; N-(2-n-propyl phenyl)-2-pyridine azomethine; N-(2-isopropyl phenyl)-2-pyridine azomethine, N-(2-n-butylphenyl)-2-pyridine azomethine, N-(2-isobutyl phenenyl)-2-pyridine azomethine; N-(2-tert-butyl-phenyl)-2-pyridine azomethine, N-(2-benzyl phenyl)-2-pyridine azomethine;
N-(2-methyl-6-ethylphenyl)-2-pyridine azomethine, N-(2-methyl-6-isopropyl phenyl)-2-pyridine azomethine, N-(2-methyl-6-isobutyl phenenyl)-2-pyridine azomethine; N-(2-methyl-6-tert butyl phenyl)-2-pyridine azomethine; N-(2-methyl-6-benzyl phenyl)-2-pyridine azomethine, N-(2-ethyl-6-isopropyl phenyl)-2-pyridine azomethine, N-(2-ethyl-6-isobutyl phenenyl)-2-pyridine azomethine; N-(2-ethyl-6-tert-butyl-phenyl)-2-pyridine azomethine; N-(2-ethyl-6-benzyl phenyl)-2-pyridine azomethine, N-(2-sec.-propyl-6-isobutyl phenenyl)-2-pyridine azomethine, N-(2-sec.-propyl-6-tert-butyl-phenyl)-2-pyridine azomethine; N-(2-sec.-propyl-6-benzyl phenyl)-2-pyridine azomethine; N-(2-isobutyl--6-tert-butyl-phenyl)-2-pyridine azomethine, N-(2-isobutyl--6-benzyl phenyl)-2-pyridine azomethine, N-(the 2-tertiary butyl-6-benzyl phenyl)-2-pyridine azomethine;
N-(2,4, the 6-trimethylphenyl)-2-pyridine azomethine, N-(2,4,6-triethyl phenyl)-2-pyridine azomethine; N-(2,4,6-triisopropyl phenyl)-2-pyridine azomethine, N-(2,4; 6-triisobutyl phenyl)-and 2-pyridine azomethine, N-(2,4,6-tri-tert phenyl)-2-pyridine azomethine, N-(2-methyl-4; The 6-3,5-dimethylphenyl)-and 2-pyridine azomethine, N-(2-methyl-4,6-diethylammonium phenyl)-2-pyridine azomethine, N-(2-methyl-4,6-dibenzyl phenyl)-2-pyridine azomethine; N-(2-sec.-propyl-4,6-3,5-dimethylphenyl)-2-pyridine azomethine, N-(2-sec.-propyl-4,6-diethylammonium phenyl)-2-pyridine azomethine, N-(2; 4-di-isopropyl-6-aminomethyl phenyl)-and 2-pyridine azomethine, N-(2,4-di-t-butyl-6-aminomethyl phenyl)-2-pyridine azomethine, N-(2,4-dibenzyl-6-aminomethyl phenyl)-2-pyridine azomethine; N-(2, the 6-3,5-dimethylphenyl)-2-pyridine ethyliminum, N-(2,6-diethylammonium phenyl)-2-pyridine ethyliminum, N-(2; The 6-diisopropyl phenyl)-and 2-pyridine ethyliminum, N-(2,6-diisobutyl phenyl)-2-pyridine ethyliminum, N-(2, the 6-di-tert-butyl-phenyl)-2-pyridine ethyliminum; N-(2,6-dibenzyl phenyl)-2-pyridine ethyliminum, N-(2, the 4-3,5-dimethylphenyl)-2-pyridine ethyliminum, N-(2; 4-diethylammonium phenyl)-and 2-pyridine ethyliminum, N-(2, the 4-diisopropyl phenyl)-2-pyridine ethyliminum, N-(2,4-diisobutyl phenyl)-2-pyridine ethyliminum; N-(2, the 4-di-tert-butyl-phenyl)-2-pyridine ethyliminum, N-(2,4-dibenzyl phenyl)-2-pyridine ethyliminum;
N-(2,4, the 6-trimethylphenyl)-2-pyridine ethyliminum, N-(2,4; 6-triethyl phenyl)-and 2-pyridine ethyliminum, N-(2,4,6-triisopropyl phenyl)-2-pyridine ethyliminum, N-(2; 4,6-triisobutyl phenyl)-2-pyridine ethyliminum, N-(2,4,6-tri-tert phenyl)-2-pyridine ethyliminum.
The detailed preparation method of pyridine-2-alkyl imines is referring to CN1331252A.
During aforesaid method (1) goes on foot, pyridine-2-alkyl group with imine moiety and TiCl
4Mol ratio be 1: 1～10, preferred 1: 1.1～5.0.The preferred C of said halogenated alkane
1～C
4Chloroparaffin, more preferably methylene dichloride or ethylene dichloride.Preferred 30～100 ℃ of the temperature of dissolving pyridine-2-alkyl group with imine moiety and reaction.
Aforesaid method (2) step is the load of catalyst activity component; Load under the unreactive hydrocarbons existence and carry out; ClMg (OR) n (ROH) that adds and the mass ratio preferred 0.2～5.0: 1 of titanium tetrachloride; The mass ratio preferred 10～60: 1 of ClMg (OR) n (ROH) and unreactive hydrocarbons, preferred 30～100 ℃ of the temperature of (2) step reaction.Remove after the load and desolvate, the gained solid washs with unreactive hydrocarbons, removes superfluous and the not firm component of load, promptly gets catalyzer after the drying.Described unreactive hydrocarbons are selected from C
5～C
10Alkane or C
6～C
8Aromatic hydrocarbons, preferred hexane, heptane, benzene or toluene.
(2) preparation method of step described magnesium-containing carrier ClMg (OR) n (ROH) is: with magnesium powder and low-carbon alcohol with 1.5～4.0: 1 ratio is in the presence of methyl halide; By a small amount of iodine is the initiator initiation reaction; Generate magnesium-containing compound solution or suspension-s; Preferred 40～100 ℃ of temperature of reaction, the reaction times is 1～20 hour, preferred 4～10 hours, the mol ratio preferred 2.0～3.0: 1 of alcohol and magnesium powder.With stable hydrocarbon the title complex in the solution is separated out, the said preferred C of stable hydrocarbon that is used to separate out carrier
5～C
8Aliphatic hydrocarbon, like pentane, hexane, heptane or octane.Separate out temperature and be-10～100 ℃, preferred 0～60 ℃, with the solid particulate of separating out and separated from solvent, drying, promptly obtain required magnesium-containing carrier, its detailed preparation method is referring to CN101117362A.
The method of using catalyzer of the present invention to carry out alpha-olefine polymerizing or copolymerization is: be Primary Catalysts with catalyzer of the present invention; With the aluminum alkyls is promotor; Terminal olefin is reacted under polymerizing condition, and the mol ratio of Ti is 25～1000, preferred 50～500 in Al during reaction in the promotor and the Primary Catalysts.
The preferred triethyl aluminum of described aluminum alkyls, triisobutyl aluminium, aluminium diethyl monochloride or ethyl aluminum dichloride.
Can adopt slurry polymerization when carrying out olefinic polymerization with catalyzer of the present invention, the solvent during polymerization can be selected alkane, aromatic hydrocarbons and halogenated alkane for use, and preferred solvent is a paraffinic hydrocarbons, like normal butane, normal hexane, normal heptane, Trimethylmethane, iso-pentane or octane-iso.Catalyzer of the present invention in addition also is applicable to the gas phase mass polymerization, like gas fluidised bed polymerisation.
The temperature of using catalyzer of the present invention to carry out alpha-olefine polymerizing or copolymerization is 10～110 ℃, preferred 20～100 ℃, and pressure is 0.1～5.0MPa, preferred 0.1～1.0MPa.When carrying out alpha-olefin copolymer, optimal ethylene and alpha-olefin copolymer, the preferred propylene of the comonomer of use, butylene, hexene or octene.
Pass through example in detail the present invention below, but the present invention is not limited to this.
In the instance, the fusing point of polymkeric substance and percent crystallinity adopt differential scanning calorimetry (DSC) to measure.Determining instrument is the TA5000DSC2910 thermal analyzer.Test condition: N
2Under the atmosphere, 10 ℃/minute of temperature rise rates, 40～300 ℃ of intensification scopes.Percent crystallinity is calculated by following formula:
Percent crystallinity=Δ H
f/ Δ H
F0* 100%
Δ H
fBe the Vilaterm melting heat that DSC records, Δ H
F0Be the heat of fusion of crystalline polyethylene, its value is 291.7J/g.
The XRN-400A fusion index instrument that the melting index of polymkeric substance (MI) adopts Chengde trier factory to produce is measured said MI
2.16Be the melting index of polymkeric substance under 2.16kg, measuring method is for being 190 ℃ in temperature, and the time is 10min, when loading to 2.16kg, when being the rheometer osculum of 0.2cm through diameter in the melt amount of gram.
Element in the instance in the catalyst sample and alkoxyl group adopt following method to measure:
Mg, Ti-adopt electric coupling plasma emission spectrometry (ICP/AES) on Varian VISTA-AX type instrument, to measure.
Nitrogen content is used chemoluminescence method, on Antek-N9000 sulphur apparatus for nitrogen examination, measures.
Alkoxyl group-employing SHIMAD2U-14B type gas chromatograph (chromatographic column: GDX-401,2.5 * 3mm, FID: hydrogen flame) measure.
Instance 1
Prepare the used carrier of catalyzer of the present invention.
Get 1.0g (41.7mmol) magnesium powder, under nitrogen protection, put into there-necked flask, add 0.1g I
2And 60mL (80g) CH
2Cl
2, stirred 5 minutes in 41 ℃, slow Dropwise 5 mL (86.1mmol) ethanol, reaction is acutely carried out and is produced great amount of bubbles.Dropwise, stirring reaction 10 hours is to magnesium powder complete reaction under this temperature.Reaction product is cooled to 25 ℃, obtains colourless transparent solution, whipped state adds the 60mL hexane down, and the adularescent crystal is separated out, and continues to stir 60 minutes.Filter, solids in 25 ℃ of dryings, is obtained the white powder crystal, be carrier A, its expression formula is ClMg (OC
2H
5) 0.63 (C
2H
5OH).
Each component concentration of carrier A is: Mg 17.52 quality %, Cl 27.71 quality %, (OC
2H
5) 53.40 quality %.
Instance 2
Method by instance 1 prepares carrier, and different is with 60mL (89g) CHCl
3Replaced C H
2Cl
2, and make magnesium powder and ethanol synthesis at 61 ℃, and making carrier B, its expression formula is ClMg (OC
2H
5) 0.81 (C
2H
5OH), each component concentration of B is in the carrier: Mg, 16.67 quality %; Cl, 20.92 quality %; (OC
2H
5), 56.40 quality %.
Instance 3
Preparation pyridine-2-group with imine moiety.
With 2 of 10mmol; 6-diisopropyl aniline (Sweden;
company) is dissolved in the 20mL methyl alcohol; 2-pyridylaldehyde (the Sweden that adds 10mmol;
company), add 5 formic acid again.Be heated to 65 ℃ of backflows 3 hours, be cooled to 25 ℃, decompression removes down and desolvates, and the gained solid is chilled to-50 ℃, washes drying under twice, 30 ℃ of decompression with 10mL-30 ℃ ethanol, gets 1.8 gram N-(2, the 6-diisopropyl phenyl) pyridines-2-azomethine.
Instance 4
Method by instance 3 prepares pyridine-2-alkyl imines, and different is to react with 2 and 2-pyridylaldehyde, gets 1.5 gram N-(2,4, the 6-trimethylphenyl) pyridines-2-azomethine.
Instance 5
Prepare catalyzer of the present invention.
(1) preparation active component solution
Get N-(2, the 6-diisopropyl phenyl) pyridine-2-azomethine 0.48g (1.9mmol) of instance 3 preparations, nitrogen protection with the dissolving of 5mL dichloromethane solution, adds 0.4mL (3.65mmol) TiCl down again
4, 50 ℃ were stirred 0.5 hour, and it were fully dissolved obtain active component solution.
(2) preparation catalyzer
In the there-necked flask that has mechanical stirring device and reflux exchanger, under the nitrogen protection, add the carrier A 1.0g of instance 1 preparation; With the abundant dispersed with stirring of 40mL hexane, add the active component solution of (1) step preparation, be warming up to 70 ℃; Continued stirring reaction 2 hours, and stopped to stir, leave standstill to the reaction solution layering; Take out supernatant liquid; Divide 3 washing precipitate to washing lotions colourless fully with the 90mL hexane, drying obtains the solid catalyst H of good fluidity, and its each component concentration is: titanium 5.64 quality %, magnesium 15.78 quality %, nitrogen 0.77 quality %.
Instance 6
Method by instance 5 prepares solid catalyst; Different is to replace N-(2 with 0.46g (2.0mmol) N-(2,4, the 6-trimethylphenyl) pyridine-2-azomethine in (1) step; The 6-diisopropyl phenyl) pyridine-2-azomethine; (2) replace carrier A with carrier B in the step, obtain catalyst I, its each component concentration is: titanium 5.68 quality %, magnesium 14.88 quality %, nitrogen 0.93 quality %.
Instance 7
Method by instance 5 prepares solid catalyst; Different is to get 0.12g (0.5mmol) N-(2 in (1) step; The 6-diisopropyl phenyl) pyridine-2-azomethine prepares active component solution; Obtain catalyzer J, its each component concentration is: titanium 4.24 quality %, magnesium 15.42 quality %, nitrogen 0.55 quality %.
Instance 8
Method by instance 5 prepares solid catalyst; Different is with 0.46g (2.0mmol) N-(2 in (1) step; 4; The 6-trimethylphenyl) pyridine-2-azomethine prepares active component solution, obtains catalyzer K, and its each component concentration is: titanium 6.01 quality %, magnesium 14.23 quality %, nitrogen 1.08 quality %.
Comparative Examples 1
Method by CN101117362A instance 6 prepares solid catalyst.
Get the 2.0g carrier A, put into the there-necked flask that has reflux exchanger and stirring, under nitrogen protection, add the 30mL hexane, stir and be warming up to 70 ℃ and process suspension-s, add 8mL (72.05mmol) TiCl
4, stirring reaction 2 hours divides washing precipitate three times with the 90mL hexane again, and drying obtains the solid catalyst O of good fluidity, and its each component concentration is: titanium 6.34 quality %, magnesium 16 quality %.
Comparative Examples 2
Prepare magnesium chloride alcohol [MgCl by CN1580084A instance 4 (1) one step process
20.36 (BuOH)] carrier.
Get the above-mentioned magnesium chloride alcohol carrier of 1.0g (10.3mmol), put into the there-necked flask that has reflux exchanger and stirring, under nitrogen protection, add the 40mL hexane; Stir and be warming up to 70 ℃ and process suspension-s, add the active component solution of instance 5 (1) step preparation, be warming up to 70 ℃; Continued stirring reaction 2 hours, and stopped to stir, leave standstill to the reaction solution layering; Take out supernatant liquid; Divide 3 washing precipitate to washing lotions colourless fully with the 90mL hexane, drying obtains the solid catalyst P of good fluidity, and its each component concentration is: titanium 5.38 quality %, magnesium 10.9 quality %, nitrogen 1.2 quality %.
Comparative Examples 3
Method by CN1580084A instance 4 prepares catalyzer.
Get 1.46g (15mmol) anhydrous magnesium chloride, put into the there-necked flask that has reflux exchanger and stirring, under nitrogen protection, add the 40mL hexane, stir and be warming up to 70 ℃ and process suspension-s, add the titanium butoxide [Ti (OBu) of 0.12mL (0.35mmol)
4], the magnesium chloride powder is fully disperseed in hexane, continuation is stirred and was reacted 1 hour down at 70 ℃, slowly drips the propyl carbinol of 0.40mL (5.4mmol), continues under this temperature, to react 1 hour, obtains activated carrier MgCl
20.36 hexane suspension-s (BuOH) is subsequent use.
N-(2, the 6-diisopropyl phenyl) pyridine-2-azomethine titanium tetrachloride of getting 1.03g (2.26mmol) fully is dissolved in 10mLCH
2Cl
2, splash into 0.5mL (4.56mL) TiCl
4Solution, 50 ℃ of stirrings were fully dissolved it in 0.5 hour and are obtained active component solution.
Above-mentioned active component solution is joined in the hexane suspension-s of activated carrier; 60 ℃ of stirring reactions 2 hours stop to stir, and leave standstill to the reaction solution layering; Take out supernatant liquid; Divide 3 washing precipitate to washing lotions colourless fully with the 90mL hexane, drying obtains the solid catalyst Q of good fluidity, and its each component concentration is: titanium 6.85 quality %, magnesium 10.7 quality %, nitrogen 1.4 quality %.
Instance 9～15
Following instance carries out the high-pressure ethylene polyreaction.
1 liter of autoclave with nitrogen pump drainage displacement three times, is used hydrogen exchange three times again, add the hexane solution and the solid catalyst 20mg of 500mL exsiccant hexane and 6mL triethyl aluminum then successively; Making the Al/Ti mol ratio is 200; Be warming up to 80 ℃, keeping the interior hydrogen partial pressure of autoclave is 0.1MPa, feeds ethene again and boosts to 0.8MPa; The reaction absolute pressure is 0.9MPa, polyreaction 1 hour.Each instance catalyst system therefor, catalyst activity and polymer property are seen table 1.
Instance 16～22
Reaction conditions by instance 9 carries out vinyl polymerization, and different is that hydrogen partial pressure is 0.2MPa, and ethylene partial pressure is 0.7MPa, and the reaction absolute pressure is 0.9MPa.Each instance catalyst system therefor, catalyst activity and polymer property are seen table 1.
Can know from table 1, adopt catalyzer of the present invention to carry out vinyl polymerization, the hydrogen partial pressure when increasing polymerization, the poly melting index of gained increases rapidly, catalyzer of the present invention is described than the comparative catalyst, and hydrogen response can be higher.
Table 1
Claims (12)
1. an olefin polymerization solid catalyst comprises that general formula is the magnesium-containing carrier of ClMg (OR) n (ROH), the pyridine shown in the formula (I)-2-alkyl imines titanium tetrachloride and TiCl
4,
Among said support C lMg (OR) n (ROH), R is selected from C
1～C
4Alkyl, n is 0.1～1.0, in the formula (I), R
1, R
2Be respectively single substituting group or multi-substituent on pyridine ring and the aniline ring, be selected from hydrogen, C respectively
1～C
6Alkyl, phenyl or C
7～C
8Aralkyl, R
3Be selected from hydrogen or C
1～C
3Alkyl, Mg content is that 2～18 quality %, titanium content are that 1.0～9.0 quality %, nitrogen content are 0.1～2.0 quality % in the said catalyzer.
2. according to the described catalyzer of claim 1, it is characterized in that R is selected from C among said support C lMg (OR) n (ROH)
1～C
3Alkyl, n is 0.5～1.0.
3. according to the described catalyzer of claim 1, it is characterized in that described ROH is ethanol, propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
4. according to the described catalyzer of claim 1, it is characterized in that in the formula (I) R
1And R
2Be selected from hydrogen or C respectively
1～C
4Alkyl, R
3Be selected from hydrogen, methyl or ethyl.
5. according to the described catalyzer of claim 1, it is characterized in that Mg content is that 2～15 quality %, titanium content are that 2.0～7.0 quality %, nitrogen content are 0.5～2.0 quality % in the said catalyzer.
6. the preparation method of the said solid catalyst of claim 1 comprises the steps:
(1) preparation active component solution: pyridine-2-alkyl group with imine moiety is dissolved in the halogenated alkane, adds TiCl
4, said pyridine-2-alkyl group with imine moiety and TiCl
4Mol ratio be 1: 1.1～15,
(2) preparation catalyzer: ClMg (OR) n (ROH) is suspended in the unreactive hydrocarbons; The active component solution that adds the preparation of (1) step; Fully after the reaction with the gained solid with unreactive hydrocarbons washing, drying, said ClMg (OR) n (ROH) is 1: 10～100 with the mass ratio of unreactive hydrocarbons, with TiCl
4Mass ratio is 0.2～15.0: 1.
7. according to the described method of claim 6, it is characterized in that described halogenated alkane is selected from C
1～C
4Chloroparaffin, described unreactive hydrocarbons are selected from C
5～C
10Alkane or C
6～C
8Aromatic hydrocarbons.
8. according to the described method of claim 6, it is characterized in that pyridine-2-alkyl group with imine moiety and TiCl in (1) step
4Mol ratio be 1: 1.1～10.0.
9. according to the described method of claim 6, it is characterized in that the mass ratio of ClMg (OR) n (ROH) and titanium tetrachloride is 0.2～5.0: 1 in (2) step.
10. according to the described method of claim 6, it is characterized in that the temperature of (2) step reaction is 30～100 ℃.
11. alpha-olefine polymerizing or process for copolymerization; Comprise that with the described solid catalyst of claim 1 be Primary Catalysts; With the aluminum alkyls is promotor, and terminal olefin is reacted under polymerizing condition, and the mol ratio of Ti is 25～1000 in Al during reaction in the promotor and the Primary Catalysts.
12., it is characterized in that described aluminum alkyls is selected from triethyl aluminum, triisobutyl aluminium or aluminium diethyl monochloride according to the described method of claim 11.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580084A (en) * | 2003-07-31 | 2005-02-16 | 中国石油化工股份有限公司 | Bi active component polyolefin catalyst, and its preparing method and use |
| CN101190953A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Process for preparing catalyst solid component of olefin polymerization |
| CN101205264A (en) * | 2006-12-22 | 2008-06-25 | 中国石油化工股份有限公司 | Ethane polymerization solid catalyst and preparation thereof |
| CN101397349A (en) * | 2007-09-28 | 2009-04-01 | 中国石油化工股份有限公司 | Ti system wide/double peak olefin polymerization catalyst, preparation and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580084A (en) * | 2003-07-31 | 2005-02-16 | 中国石油化工股份有限公司 | Bi active component polyolefin catalyst, and its preparing method and use |
| CN101190953A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Process for preparing catalyst solid component of olefin polymerization |
| CN101205264A (en) * | 2006-12-22 | 2008-06-25 | 中国石油化工股份有限公司 | Ethane polymerization solid catalyst and preparation thereof |
| CN101397349A (en) * | 2007-09-28 | 2009-04-01 | 中国石油化工股份有限公司 | Ti system wide/double peak olefin polymerization catalyst, preparation and use |
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