CN1580084A - Bi active component polyolefin catalyst, and its preparing method and use - Google Patents
Bi active component polyolefin catalyst, and its preparing method and use Download PDFInfo
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- CN1580084A CN1580084A CN 03149937 CN03149937A CN1580084A CN 1580084 A CN1580084 A CN 1580084A CN 03149937 CN03149937 CN 03149937 CN 03149937 A CN03149937 A CN 03149937A CN 1580084 A CN1580084 A CN 1580084A
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Abstract
A kind of dual-active catalyst composed of polyolefin includes MgCl2.n(ROH), TiCl4 and pyridine-2-alkyl-imine-TiCl4 demonstrated in the molecular formula (1) and the R1 and R2 in the molecular formula (1) are single-substituents or poly-substituents in the cycles of pyridine and aniline respectively which are derived from hydrogen, alkyls between C1 and C6 or aralkyls between C7 and C8. This catalyst has a dual-active center and can get double-humped or broad-molecular-weighted olefin polymer, which is featured with single high melting-point and high crystallizing point.
Description
Technical field
The present invention specifically, is a kind of with TiCl for the olefin polymerization catalysis and the preparation method of load dual-active component
4With bidentate coordinate titanium compound nitrogenous in the part be catalyzer and the preparation method and the application of active ingredient.
Background technology
In the course of processing of polyolefine material, polyolefinic molecular weight has a significant impact processing characteristics as poly molecular weight and molecular weight distribution.Under the certain situation of polyolefine weight-average molecular weight, molecular weight distribution is determining its physicals, mechanical property and rheological property.Molecular weight distribution is wide then to help materials processing, and narrow molecular weight distribution then is unfavorable for the processing of material.Recently contain heteroatomic non-metallocene catalyst in the part of development, have high polymerization activity, but need use expensive methylaluminoxane to be promotor during polymerization.Disclosed a kind of to have bidentate coordinate pyridine imine be the transition metal complex of part as CN1331252A, when this title complex is used for vinyl polymerization as catalyzer, can obtain the high-molecular weight polymerisate, but the molecular weight distribution of product is still wide inadequately, when particularly being made into loaded catalyst, the molecular weight distribution of the polymerisate that obtains is narrower.
A kind of method of improving molecular weight distribution is that preparation has polymkeric substance bimodal or the broad peak molecular weight distribution.This polymkeric substance is made up of the polyolefine that two kinds of different molecular weights distribute, and that is to say by a kind of molecular weight distribution higher relatively polyolefine and the relatively low polyolefine of a kind of molecular weight distribution and forms.Polyolefine advantage bimodal or the broad peak molecular weight distribution is that it had both kept the premium properties of high molecular part, comprise tensile strength, extension at break, impact-resistance and puncture resistance, again because of existing low molecular weight part to improve processing characteristics, extrusion performance especially.In the prior art, often the supported catalyst that has two kinds of active ingredients by preparation prepares and has polymkeric substance bimodal or the broad peak molecular weight distribution.
Summary of the invention
The purpose of this invention is to provide a kind of polyolefin catalyst and preparation method who contains the dual-active component, this catalyzer is used for olefinic polymerization, has high polymerization activity, and the polyolefine of producing has wider molecular weight distribution.
Dual-active component polyolefin catalyst provided by the invention comprises carrier MgCl
2N (ROH), TiCl
4And the pyridine shown in the formula (I)-2-alkyl imines titanium tetrachloride,
R in the formula (I)
1, R
2Be respectively single substituting group or multi-substituent on pyridine ring and the aniline ring, be selected from hydrogen, C independently of one another
1～C
6Alkyl or C
7～C
8Aralkyl, carrier MgCl
2N is 0.1～2.0 among the n (ROH), and R is C
2～C
8Alkyl; Mg content is 5～20 quality % in the described catalyzer, and titanium content is 0.5～12 quality %, TiCl
4With the mol ratio of pyridine-2-alkyl imines titanium tetrachloride be 0.1～5.0: 1.
The present invention adopts two kinds of active ingredients to prepare the catalyzer of load, makes this catalyzer have double activity center, therefore, can make the polymkeric substance that is bimodal or wide molecular weight distribution, described polymkeric substance has single high-melting-point and high-crystallinity, and degree of crystallinity is up to 87.1% generally greater than 65%.
Description of drawings
Fig. 1 is differential scanning (DSC) figure with the polymkeric substance of Preparation of Catalyst of the present invention.
Fig. 2 is gel permeation chromatography figure (GPC) figure with the polymkeric substance of Preparation of Catalyst of the present invention.
Embodiment
Two kinds of active ingredients in the catalyzer of the present invention, a kind of is conventional Ziegler-Natta catalyst component TiCl
4, another kind is bidentate coordinate titanium compound pyridine-2-alkyl imines titanium tetrachloride.TiCl in the catalyzer
4Should be controlled at certain limit, preferred 0.4～3.0: 1 with the mol ratio of pyridine-2-acyl group imines titanium tetrachloride.TiCl in the catalyzer
4Content is too high, will make molecular weight distribution narrow down TiCl
4Content is too low, and then catalytic activity significantly descends.Preferred 2.0～5.0 quality % of titanium content in the catalyzer, preferred 5～13 quality % of Mg content.
In described active ingredient pyridine-2-alkyl imines titanium tetrachloride, R
1And R
2Be respectively the substituting group on pyridine ring and the aniline aromatic ring, the substituent R on the pyridine ring
1Number can be 1～3, replace the position and be preferably 4 or 6 of pyridine ring.Substituent R on the aniline aromatic ring
2Number be 1～6, preferred 1～3, replace the position and preferably be positioned at 2,4,6 of phenyl ring.R
1And R
2The preferred hydrogen of difference, C
1～C
4Alkyl, phenyl or benzyl, more preferably hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl.R
3Be the substituting group on the imines carbon atom, preferred hydrogen, methyl or ethyl.
Ligand compound in pyridine-2-alkyl imines titanium tetrachloride that the present invention uses is preferred: N-(2, the 6-3,5-dimethylphenyl)-and 2-pyridine azomethine, N-(2,6-diethyl phenyl)-2-pyridine azomethine, N-(2, the 6-diisopropyl phenyl)-and 2-pyridine azomethine, N-(2,6-diisobutyl phenyl)-2-pyridine azomethine, N-(2, the 6-di-tert-butyl-phenyl)-and 2-pyridine azomethine, N-(2,6-dibenzyl phenyl)-2-pyridine azomethine, N-(2, the 4-3,5-dimethylphenyl)-and 2-pyridine azomethine, N-(2,4-diethyl phenyl)-2-pyridine azomethine, N-(2, the 4-diisopropyl phenyl)-and 2-pyridine azomethine, N-(2,4-diisobutyl phenyl)-2-pyridine azomethine, N-(2, the 4-di-tert-butyl-phenyl)-and 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)-2-pyridine azomethine, N-(2,4,6-tri-tert phenyl)-and 2-pyridine azomethine, N-(2-methyl-4,6-3,5-dimethylphenyl)-2-pyridine azomethine, N-(2-methyl-4,6-diethyl phenyl)-and 2-pyridine azomethine, N-(2-methyl-4,6-dibenzyl phenyl)-2-pyridine azomethine, N-(2-sec.-propyl-4, the 6-3,5-dimethylphenyl)-and 2-pyridine azomethine, N-(2-sec.-propyl-4,6-diethyl 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)-and 2-pyridine ethyliminum, N-(2,6-diethyl 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)-and 2-pyridine ethyliminum, N-(2,6-dibenzyl phenyl)-2-pyridine ethyliminum, N-(2, the 4-3,5-dimethylphenyl)-and 2-pyridine ethyliminum, N-(2,4-diethyl phenyl)-2-pyridine ethyliminum, N-(2, the 4-diisopropyl phenyl)-and 2-pyridine ethyliminum, N-(2,4-diisobutyl phenyl)-2-pyridine ethyliminum, N-(2, the 4-di-tert-butyl-phenyl)-and 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)-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.
Support of the catalyst MgCl of the present invention
2N among the n (ROH) is preferred 0.1～1.0, the preferred C of described alcohol
2～C
6Fatty Alcohol(C12-C14 and C12-C18) is arranged, as ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol or hexanol.
Described Preparation of catalysts method comprises:
(1) preparation carrier MgCl
2The suspension of n (ROH) in unreactive hydrocarbons solvent, n is 0.1～2.0 in the carrier, R is C
2～C
8Alkyl;
(2) with making solution in the pyridine shown in the formula (I)-2-alkyl imines titanium tetrachloride adding organic solvent, add TiCl again
4, make TiCl
4With the mol ratio of the pyridine shown in the formula (I)-2-alkyl imines titanium tetrachloride be 0.1～5.0: 1,
(3) solution made of (2) step is joined in the suspension that (1) step makes, fully stirs in 0～150 ℃ and make carrier and the abundant contact reacts of active ingredient, then with unreactive hydrocarbons solvent wash, drying.
In the described method, (1) step, used carrier prepared by two kinds of diverse ways.A kind of is the method preparation of adopting the adducts dealcoholysis that makes magnesium chloride alcohol, and promptly the alcohol with q.s dissolves Magnesium Chloride Anhydrous fully, obtains MgCl after the drying
2(ROH) adducts, and then with the heating dealcoholysis of this adducts or use organic compound is sloughed wherein alcohol as aluminum alkyls, makes activated carrier.When using this carrier loaded active ingredient, need carrier is dissolved in suspension in the unreactive hydrocarbons solvent, load active component again.
As carrier MgCl
2N is 0.1～1.0 o'clock among the n (ROH), can adopt the method activation magnesium chloride of direct alcoholization.Activation method is: with anhydrous MgCl
2Be suspended in the unreactive hydrocarbons solvent, elder generation carries out Magnesium Chloride Anhydrous at 30～200 ℃ of adding dispersion agents pre-dispersed, and then adds C
2～C
8Alcohol activate, wherein the mol ratio of dispersion agent and Magnesium Chloride Anhydrous is 0.01～2.0, it is Ti (OR ') that dispersion agent is selected from general formula
4Alkoxy titanium compound or C
3～C
8Alcohol, wherein R ' is C
2～C
6Alkyl.The preferred ethanolato-titanium of dispersion agent, titanium propanolate or titanium butoxide.Detailed preparation method is referring to CN1264713A.Because the activated carrier that aforesaid method makes does not need dealcoholysis, the unreactive hydrocarbons suspension load active component that forms in the time of can directly utilizing its preparation.
(2) step is that preparation is used for the active component solution of load in the inventive method, and used organic solvent should be able to the lytic activity component during preparation, is beneficial to active centre uniform distribution on carrier.The quantity of solvent of using is 5～150 times of the active ingredient total amount, preferred 10～50 times.Preferred organic is C
1～C
4Halogenated alkane, benzene, toluene or dimethylbenzene, preferred C
1～C
4Chloroparaffin or toluene, more preferably methylene dichloride or ethylene dichloride.With the temperature of organic solvent dissolution active ingredient preferred 30～100 ℃, preferred 0.1～1.5 hour of dissolution time.
(3) step of described method is the load of active ingredient, preferred 30～100 ℃ of load temperature, preferred 0.5～12 hour of time suitably increased load time and helps active ingredient and fully be carried on the carrier, and the active centre of avoiding catalyzer to cause in polymerization process comes off.Remove after the load and desolvate, the gained solid washs with unreactive hydrocarbons, removes component not strong for load, promptly gets catalyzer after the drying.
Load or wash used unreactive hydrocarbons solvent and be selected from C among the described preparation method
5～C
15Alkane or C
6～C
8Aromatic hydrocarbons, preferred C
5～C
12Alkane, be preferably hexane, heptane, octane and decane.
The preparation method of active ingredient pyridine of the present invention-2-alkyl imines titanium tetrachloride is: with TiCl
4Or TiCl
4Be dissolved in the adducts made behind the ether solvents and pyridine-2-alkyl imine derivative by etc. the amount of mol ratio in organic solvent, react, reaction finishes, and promptly gets catalyzer after collecting solid, drying.Described organic solvent is selected from C
1～C
4Chloroparaffin, C
1～C
4Alcohol or C
6～C
12Aromatic hydroxy compound, preferred methylene dichloride, ethylene dichloride, toluene or dimethylbenzene.Detailed preparation method is referring to CN1331252A.
Catalyzer of the present invention is applicable to vinyl polymerization or makes ethene and at least a C
3～C
8Alpha-olefin carry out copolymerization, during polymerization with alkylaluminoxane, aluminum alkyls, alkyl aluminum halide or in them arbitrarily two or more mixture be promotor, the mol ratio of Al/Ti is 20～2000 during polymerization, is preferably 25～1000.Polymerization temperature is 10～110 ℃, and preferred 20～100 ℃, polymerization pressure is 0.1～8.0MPa, preferred 0.1～1.0MPa.
Described promotor preferable methyl aikyiaiurnirsoxan beta, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride or two or more mixture arbitrarily in them.The preferred propylene of comonomer when ethene and alpha-olefin carry out copolymerization, butylene, hexene or octene.
Can adopt slurry polymerization when carrying out olefinic polymerization with catalyzer of the present invention, solvent during polymerization can be selected alkane, aromatic hydrocarbons and halogenated alkane for use, and preferred solvent is a linear paraffinic hydrocarbons, as n-butane, n-hexane and n-heptane, or branched paraffin, as Trimethylmethane, iso-pentane, octane-iso.Catalyzer of the present invention in addition also is applicable to the gas phase mass polymerization, as gas fluidised bed polymerisation.
Below by example in detail the present invention, but the present invention is not limited to this.
The fusing point of polymkeric substance and degree of crystallinity adopt differential scanning calorimetry (DSC) to measure in the example.Determining instrument is a TA5000 DSC2910 thermal analyzer.Test condition: N
2Under the atmosphere, 10 ℃/minute of temperature rise rates, 40～300 ℃ of intensification scopes.Degree of crystallinity is calculated by following formula:
X％＝ΔH
f/ΔH
f0×100％
Δ H
fThe polyethylene melting heat that records for DSC,
Δ H
F0Be the heat of fusion of crystalline polyethylene, its value is 291.7J/g.
The molecular weight of polymkeric substance and molecular weight distribution are measured with gel permeation chromatography (GPC), and used instrument is the Alliance GPC2000 type gel permeation chromatograph of U.S. Waters company.
Example 1
Preparation N-(2, the 6-diisopropyl phenyl)-2-pyridine azomethine titanium tetrachloride [(iPr
2Ph) PyH] TiCl
4
(1) preparation N-(2, the 6-diisopropyl phenyl) pyridine-2-azomethine (iPr
2Ph) PyH
With 2 of 10mmol, 6-diisopropyl aniline (Sweden, Acr s company) is dissolved in the 20ml methyl alcohol, adds the 2-pyridylaldehyde (Sweden, Acr s company) of 10mmol, adds 5 formic acid again.Be heated to 65 ℃ and refluxed 3 hours, be cooled to room temperature, under reduced pressure remove and desolvate, the gained solid is chilled to-50 ℃, wash twice, 30 ℃ of vacuum-drying, get 1.8 gram N-(2, the 6-diisopropyl phenyl) pyridine-2-azomethine [(iPr with 10ml-30 ℃ ethanol
2Ph) PyH], productive rate is 68 quality %.
(2) preparation [(iPr
2Ph) PyH] TiCl
4
Ice bath also stirs down, splashes into the tetrahydrofuran (THF) of 4.5mmol in the 20ml toluene solution that contains the 2.1mmol titanium tetrachloride, and room temperature reaction 4 hours filters, 30 ℃ of vacuum-drying 2 hours, 0.68 gram yellow solid TiCl
42THF, productive rate are 97 quality %.
TiCl with 2.1mmol
42THF is added in the 20ml methylene dichloride, and stirring and dissolving adds and contains 2.1mmol (iPr
2Ph) the dichloromethane solution 10ml of PyH, 25 ℃ were refluxed 18 hours down, and cooling is filtered, and solid is washed twice, 30 ℃ of vacuum-drying 2 hours with the 10ml ether respectively, gets 0.72 gram yellow-green colour solid complexes a:[(iPr
2Ph) PyH] TiCl
4, structural formula is as follows, and productive rate is 75 quality %.
Example 2
Method by example 1 prepares N-(2,4, the 6-trimethylphenyl)-2-pyridine azomethine titanium tetrachloride, different is to use the 2 of 10mmol to replace 2, the 6-diisopropyl aniline reacts, and obtains having the titanium complex b of following structure, and productive rate is 60 quality %.
Example 3
Method by example 1 prepares N-(2, the 6-diisopropyl phenyl)-2-pyridine ethyl imines titanium tetrachloride, is not both (1) step to replace 2-formaldehyde pyridine to react with 2-acetopyridine, obtains having the titanium complex c of following structural formula, and productive rate is 72 quality %.
Example 4
Prepare catalyzer of the present invention.
(1) preparation activated carrier
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 make suspension, add the titanium butoxide [Ti (OBu) of 0.12ml (0.35mmol)
4], making the fully dispersion in hexane of magnesium chloride powder, continuation is stirred and 70 ℃ of reactions 1 hour, is slowly dripped the propyl carbinol of 0.40ml (5.4mmol), continues to react 1 hour under this temperature, gets activated carrier MgCl
20.36 hexane suspension (BuOH).
(2) load active component
Get in the phial that band that title complex a1.03g (2.26mmol) that example 1 makes adds 50ml stirs, use nitrogen replacement, add 10mlCH after removing moisture in the system and air
2Cl
2, stir and make title complex a dissolving, splash into 0.5ml (4.56mmol) TiCl
4Solution, 50 ℃ are stirred the solution that made its dissolving obtain containing active ingredient in 0.5 hour.
The above-mentioned drips of solution that contains active ingredient is added in the activated carrier hexane suspension of (1) step preparation, 60 ℃ of stirring reactions 2 hours, stop to stir, leave standstill to the reaction solution layering, take out supernatant liquid, divide three washing precipitates colourless fully to washing lotion with the 90ml hexane again, drying under reduced pressure obtains the solid catalyst A of good fluidity, wherein titanium content is 6.85 quality %, and Mg content is 10.7 quality %.
Example 5
Method by example 4 prepares catalyst B, and that different is TiCl
4The add-on of solution is 0.10ml (0.92mmol).The titanium content of catalyst B is 4.51 quality %, and Mg content is 11.5 quality %.
Example 6
Method by example 4 prepares catalyzer C, and that different is TiCl
4The add-on of solution is 0.25ml (2.26mmol).The titanium content of catalyzer C is 4.83 quality %, and Mg content is 11.0 quality %.
Example 7
Method by example 4 prepares catalyzer D, and different is that the title complex that adds is b, and add-on is 0.95g (2.26mmol), TiCl
4The add-on of solution is 0.25ml (2.26mmol).The titanium content of catalyzer D is 4.97 quality %, and Mg content is 11.2 quality %.
Example 8
Method by example 4 prepares catalyzer E, and different is that the title complex that adds is c, and add-on is 1.06g (2.26mmol), TiCl
4The add-on of solution is 0.25ml (2.26mmol).The titanium content of catalyzer E is 4.61 quality %, and Mg content is 10.8 quality %.
Example 9
(1) preparation activated carrier
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 reflux temperature and make suspension; 70 ℃ add 4.74g propyl carbinol (60mmol), stir magnesium chloride is dissolved fully removal of solvent under reduced pressure; solids 150 ℃ of heating dealcoholysis, is obtained carrier MgCl
21.5 (BuOH).
(2) load active component
With 1.8g carrier MgCl
21.5 (BuOH) join in the 40ml hexane and make suspension.Get title complex a 1.03g (2.26mmol) the adding 10mlCH that example 1 makes again
2Cl
2, stirring splashes into 0.5ml (4.56mmol) TiCl after making its dissolving again
4Solution, 50 ℃ are stirred the solution that obtained containing active ingredient in 0.5 hour.This drips of solution is added in the above-mentioned carrier suspension that makes, 60 ℃ of stirring reactions 2 hours, leave standstill to the reaction solution layering, take out supernatant liquid, divide three washing precipitates colourless fully with the 90ml hexane again to washing lotion, drying under reduced pressure obtains the solid catalyst F of good fluidity, and wherein titanium content is 4.87 quality %, and Mg content is 6.0 quality %.
Comparative Examples 1
Method by example 4 prepares catalyzer M, and the active ingredient of load that different is is TiCl
4, the catalyzer M titanium content that obtains is 6.41 quality %, Mg content is 13.2 quality %.
Comparative Examples 2
Method by example 4 prepares catalyst n, and the active ingredient of load that different is is N-(2, the 6-diisopropyl phenyl)-2-pyridine azomethine titanium tetrachloride, and the catalyst n titanium content that obtains is 2.29 quality %, and Mg content is 19.4 quality %
Example 10～17
Following example carries out the high-pressure ethylene polyreaction.
1 liter of autoclave is replaced three times with the nitrogen pump drainage, with the ethene displacement once, add the hexane solution and the 38mg solid catalyst of 300ml exsiccant hexane, 11ml triethyl aluminum then successively again, be warming up to 70 ℃, feed ethene again and boost to 0.8MPa, polyreaction 0.5 hour.Each example catalyst system therefor, catalyst activity and polymer property see Table 1.
Example 18～20
Method by example 10 is carried out ethylene polymerization, and different is to feed hydrogen before feeding ethene, keeps certain hydrogen dividing potential drop in the polymerization process, and total pressure still is maintained 0.8MPa.Each example catalyst system therefor, hydrogen dividing potential drop and resulting polymers character see Table 2, wherein use the DSC spectrogram and the GPC spectrogram of the polyethylene product of catalyzer C preparation to see Fig. 1, Fig. 2 respectively.
Example 21～22
Carry out the ethylene copolymer reaction with catalyzer of the present invention.
Method by example 10 is carried out polyreaction, adds 10ml 1-hexene during reaction that different is, and feed hydrogen in reactor, and making the hydrogen dividing potential drop is 0.1MPa, 70 ℃ of following polyreactions 0.5 hour, and catalyst activity and polymer property see Table 2.
Example 23
Method by example 10 is carried out polyreaction, and different is, and to add 18ml concentration be that the toluene solution of the methylaluminoxane of 10 quality % is a promotor, and catalyst activity and polymer property see Table 2.
Example 24
Method by example 10 is carried out ethylene polymerization with catalyst A, and different is that polymerization temperature is 50 ℃, and the pressure that feeds ethene is 0.1MPa.Catalyst activity is 2.32 * 10
5GPE (molTihr)
-1
Table 1
| Instance number | The catalyzer numbering | Catalytic activity [* 10 6gPE·(molTi·hr) -1] | Fusing point, ℃ | Degree of crystallinity, % | ??M w， ??(×10 4) | ????M w/M n |
| ??10 | ??A | ??3.30 | ????133.9 | ??78.3 | ??49.0 | ????59.56 |
| ??11 | ??B | ??3.18 | ????132.64 | ??79.4 | ??31.4 | ????39.50 |
| ??12 | ??C | ??3.10 | ????133.9 | ??79.1 | ??125.7 | ????34.53 |
| ??13 | ??D | ??0.75 | ????133.7 | ??68.3 | ??76.3 | ????103.60 |
| ??14 | ??E | ??2.48 | ????130.7 | ??73.5 | ??48.9 | ????12.98 |
| ??15 | ??F | ??0.84 | ????130.02 | ??65.2 | ??65.3 | ????9.72 |
| ??16 | ??M | ??2.16 | ????133.2 | ??73 | ??65.9 | ????7.73 |
| ??17 | ??N | ??1.10 | ????134.2 | ??69.0 | ??94.1 | ????7.15 |
Table 2
| Instance number | The catalyzer numbering | The hydrogen dividing potential drop, MPa | Catalytic activity [* 10 6gPE·(molTi·hr) -1] | Fusing point, ℃ | Degree of crystallinity, % | ???M w， ???(×10 4) | ????M w/M n |
| ??18 | ????A | ????0.2 | ????2.91 | ??133.77 | ????87.1 | ???6.8 | ????15.20 |
| ??19 | ????B | ????0.1 | ????2.51 | ??133.65 | ????81.0 | ???14.0 | ????21.84 |
| ??20 | ????C | ????0.1 | ????2.45 | ??133.92 | ????78.5 | ???17.2 | ????28.18 |
| ??21 | ????A | ????0.1 | ????2.34 | ??129.81 | ????68.5 | ???10.2 | ????15.82 |
| ??22 | ????B | ????0.1 | ????1.32 | ??130.77 | ????73.5 | ???12.7 | ????12.98 |
| ??23 | ????A | ????- | ????1.61 | ??132.16 | ????74.8 | ???39.3 | ????10.50 |
Claims (12)
1, a kind of dual-active component polyolefin catalyst comprises carrier MgCl
2N (ROH), TiCl
4And the pyridine shown in the formula (I)-2-alkyl imines titanium tetrachloride,
R in the formula (I)
1, R
2Be respectively single substituting group or multi-substituent on pyridine ring and the aniline ring, be selected from hydrogen, C independently of one another
1～C
6Alkyl or C
7～C
8Aralkyl, carrier MgCl
2N is 0.1～2.0 among the n (ROH), and R is C
2～C
8Alkyl; Titanium content is 0.5～12 quality % in the described catalyzer, and Mg content is 5～20 quality %, TiCl
4With the mol ratio of pyridine-2-alkyl imines titanium tetrachloride be 0.1～5.0: 1.
2, according to the described catalyzer of claim 1, it is characterized in that R
1And R
2Be selected from hydrogen or C respectively
1～C
4Alkyl, R
3Be hydrogen, methyl or ethyl, TiCl in the catalyzer
4With the mol ratio of pyridine-2-alkyl imines titanium tetrachloride be 0.4～3.0: 1.
3,, it is characterized in that described carrier MgCl according to the described catalyzer of claim 1
2N is 0.1～1.0 among the n (ROH), and described alcohol is selected from ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol or hexanol, and titanium content is 2.0～5.0 quality % in the catalyzer, and Mg content is 5～13 quality %.
4, the described Preparation of catalysts method of a kind of claim 1 comprises:
(1) preparation carrier MgCl
2The suspension of n (ROH) in unreactive hydrocarbons solvent, n is 0.1～2.0 in the carrier, R is C
2～C
8Alkyl;
(2) with making solution in the pyridine shown in the formula (I)-2-alkyl imines titanium tetrachloride adding organic solvent, add TiCl again
4, make TiCl
4With the mol ratio of the pyridine shown in the formula (I)-2-alkyl imines titanium tetrachloride be 0.1～5.0: 1,
(3) solution made of (2) step is joined in the suspension that (1) step makes, fully stirs in 0～150 ℃ and make carrier and the abundant contact reacts of active ingredient, then with unreactive hydrocarbons solvent wash, drying.
5, in accordance with the method for claim 4, it is characterized in that (1) step preparation carrier MgCl
2The method of n (ROH) suspension is with anhydrous MgCl
2Be suspended in the unreactive hydrocarbons solvent, elder generation carries out Magnesium Chloride Anhydrous at 30～200 ℃ of adding dispersion agents pre-dispersed, and then adds C
2～C
8Alcohol activate, wherein the mol ratio of dispersion agent and Magnesium Chloride Anhydrous is 0.01～2.0, it is Ti (OR ') that dispersion agent is selected from general formula
4Alkoxy titanium compound or C
3～C
8Alcohol, wherein R ' is C
2～C
6Alkyl, n is 0.1～1.0 in the described carrier, alcohol is selected from ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol or hexanol.
6, in accordance with the method for claim 5, it is characterized in that described dispersion agent is selected from ethanolato-titanium, titanium propanolate or titanium butoxide.
7,, it is characterized in that described unreactive hydrocarbons solvent is selected from C according to claim 4 or 5 described methods
5～C
15Alkane or C
6～C
8Aromatic hydrocarbons.
8, in accordance with the method for claim 4, it is characterized in that (1) described carrier is made through hot dealcoholysis by the adducts of magnesium chloride alcohol.
9, in accordance with the method for claim 4, it is characterized in that described organic solvent of (2) step is selected from C
1～C
4Chloroparaffin, benzene, toluene or dimethylbenzene.
10, in accordance with the method for claim 4, it is characterized in that the temperature that carrier contacts with active ingredient in (3) step is 30～100 ℃, the reaction times is 0.5～12 hour.
11, the method for a kind of alpha-olefine polymerizing or copolymerization, comprise that with the described catalyzer of claim 1 be Primary Catalysts, with alkylaluminoxane, aluminum alkyls, alkyl aluminum halide or any two or more the mixture in them is promotor, alpha-olefin is reacted under polymerizing condition, and the Al/Ti mol ratio is 25～1000 during reaction.
12, according to the described polymerization process of claim 11, it is characterized in that described alkylaluminoxane is a methylaluminoxane, aluminum alkyls is triethyl aluminum, triisobutyl aluminium, alkyl aluminum halide is an aluminium diethyl monochloride, alpha-olefin is ethene, propylene or butylene, and comonomer is selected from butylene, hexene or octene.
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| CN 03149937 CN1292007C (en) | 2003-07-31 | 2003-07-31 | Bi active component polyolefin catalyst, and its preparing method and use |
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|---|---|---|---|
| CN 03149937 CN1292007C (en) | 2003-07-31 | 2003-07-31 | Bi active component polyolefin catalyst, and its preparing method and use |
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