CN100549038C - A kind of preparation method of polyethylene catalysts of loaded by semi-metallocene - Google Patents
A kind of preparation method of polyethylene catalysts of loaded by semi-metallocene Download PDFInfo
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- CN100549038C CN100549038C CNB2006100664436A CN200610066443A CN100549038C CN 100549038 C CN100549038 C CN 100549038C CN B2006100664436 A CNB2006100664436 A CN B2006100664436A CN 200610066443 A CN200610066443 A CN 200610066443A CN 100549038 C CN100549038 C CN 100549038C
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Abstract
A kind of preparation method of polyethylene catalysts of loaded by semi-metallocene comprises Magnesium Chloride Anhydrous is suspended in the unreactive hydrocarbons solvent, with Ti (OR
1)
4And C
2～C
8The abundant contact reacts of Fatty Alcohol(C12-C14 and C12-C18), obtain carrier after the drying, above-mentioned dry back carrier is handled after drying with aluminum alkyls in the presence of unreactive hydrocarbons solvent, again in the presence of polar organic solvent, with the abundant contact reacts of semi-metallocene active ingredient, collect the solids after drying, in the formula (I) with formula (I) expression formula, R and R ' can be identical or inequality, are C
1～C
12Alkyl, C
6～C
9Alkaryl or C
1～C
12Perfluoroalkyl, Cp ' has 1～5 substituent R for containing the ligand groups of cyclopentadienyl skeleton on the cyclopentadienyl skeleton
2, two adjacent substituting groups can be connected with each other and form the above condensed ring of binary, R on its skeleton
2Be selected from C
1～C
18Alkyl or perfluoroalkyl, C
6～C
24Aralkyl or alkaryl, X is a halogen, n is 1～3 integer.The catalyzer of this method preparation carries titanium amount height, and the resulting polymers particle form is good.
Description
Technical field
The present invention is a kind of preparation method of polyethylene catalysts of loaded by semi-metallocene.Specifically, be the preparation method of the polyethylene catalysts of a kind of load semi-metallocene active ingredient of containing the beta-diketo derivative part.
Background technology
After metallocene catalyst, the Nonmetallocene compound that contains coordination heteroatom ligands such as aerobic, nitrogen in the another kind of conjugated system more and more causes people's attention and concern in the application aspect polyolefine, the especially polyethylene catalysts.The Nonmetallocene compound that contains Sauerstoffatom in the part, as being that the titanium compound of part can only be used for styrene polymerization usually with beta-diketon and derivative, disclosing a kind of as CN1158859A is the catalyst system of the synthesis of syndiotactic polystyrene of Primary Catalysts with the beta-diketon titanium chloride.Its preferred Primary Catalysts is methyl ethyl diketone titanium chloride and diphenylpropane-1,3-dione(DPPO) titanium chloride.This catalyzer can prepare normality and the higher polystyrene of heat resisting temperature between height.
Usually wanting loadization, loadization during metallocene and non-metallocene catalyst are used is in order to satisfy more polymerization technique process, as the operational requirement of vapour phase polymerization, slurry polymerization.Simultaneously, loadization can improve the catalytic efficiency of active ingredient, can increase the stability in active centre, improve the form of polymkeric substance, improve the apparent density of polymkeric substance, the loadization of metallocene and non-metallocene catalyst can also reduce the consumption of promotor significantly, reduces catalyst production cost.Usually the load of metallocene or non-luxuriant polyolefin catalyst, all are first composite reactive components, be metallocene or non-half metallocene, and then title complex loaded on form supported catalyst on the carrier, disclosing a kind of as USP5869417 is active ingredient with the metallocene, molecular sieve is the preparation method of the loaded catalyst of carrier, and the used carrier of this patent is for having 7～15
The macroporous structure molecular sieve in aperture, as faujusite, SAPO-37 etc., the catalyzer that load metallocene makes on above-mentioned molecular sieve carrier can be used for ethene, propylene or cinnamic polymerization.
CN1461756A discloses a kind of non-metallocene catalyst and loaded catalyst thereof; the part of this catalyzer is the acyl-naphthaline phenolic compound; the an alkali metal salt of catalyzer employing acyl group naphthols and transition metal halide react at a lower temperature and make; its loaded catalyst is that described Nonmetallocene active ingredient solids is dispersed in the solvent, makes with the carrier reaction again.
CN1418227A discloses a kind of preceding body catalyst that comprises bidentate ligand that contains, and preceding body catalyst forms supported catalyst with the carrier reaction earlier with after the aluminum alkyls effect again.People such as K.Soga are at J.Polyrn.Sci., Polym.Chem.Ed.35, the polymerization that the cyclopentadiene titanous chloride is carried on the catalyzer that makes on the magnesium chloride support discussed in the article that 291-297 delivers, this catalyzer and triisobutyl aluminum cocatalyst are used and can prepare polypropylene, and have high polymerization activity.
CN00124667.4 discloses ethylene rolymerization catalyst and the preparation method that a kind of semi-metallocene catalyst active constituent loading that will contain the beta-diketo derivative part makes on butter, but owing to be the method that adopts co-precipitation, therefore the granules of catalyst form that makes with this method is bad, and there is saturation value during load active component, cause charge capacity limited, it is lower that the loaded catalyst that makes carries the titanium amount, therefore the polymerization efficiency of unit mass catalyzer is not high, the resulting polymers bulk density is low, and form is bad.
CN1128822C discloses a kind of preparation method of carrier for olefin polymerization catalyst, is Magnesium Chloride Anhydrous is suspended in the unreactive hydrocarbons solvent, and is pre-dispersed with alkoxy titanium compound earlier, uses C again
2～C
8Alcohol activate, the mol ratio of used alcohol and Magnesium Chloride Anhydrous is 0.05～2.5.The carrier that makes need not the solid ingredient that dealcoholysis gets final product direct load Ziegler-Natta type catalyzer.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of polyethylene catalysts of loaded by semi-metallocene, the loaded catalyst of this method preparation has advantages of high catalytic activity.
The preparation method of the polyethylene catalysts of loaded by semi-metallocene provided by the invention comprises the steps:
(1) Magnesium Chloride Anhydrous is suspended in the unreactive hydrocarbons solvent, in 30～200 ℃ and Ti (OR
1)
4And C
2～C
8The abundant contact reacts of Fatty Alcohol(C12-C14 and C12-C18), then solid drying is obtained carrier, described Ti (OR
1)
4With the mol ratio of Magnesium Chloride Anhydrous be 0.01～0.2, Fatty Alcohol(C12-C14 and C12-C18) and Magnesium Chloride Anhydrous mol ratio are 0.1～1.0, formula Ti (OR
1)
4In R
1Be selected from C
1～C
7Alkyl;
(2) (1) step dry back carrier is handled after drying with aluminum alkyls in the presence of unreactive hydrocarbons solvent, the mol ratio of aluminum alkyls and magnesium chloride is 0.1～2.0;
(3) in the presence of polar organic solvent, magnesium chloride support that will obtain after will handling with aluminum alkyls and the abundant contact reacts of semi-metallocene active ingredient with formula (I) expression formula are collected the solids after drying,
In the formula (I), R and R ' can be identical or inequality, are C
1～C
12Alkyl, C
6～C
9Alkaryl or C
1～C
12Perfluoroalkyl, Cp ' has 1～5 substituent R for containing the ligand groups of cyclopentadienyl skeleton on the cyclopentadienyl skeleton
2, two adjacent substituting groups can be connected with each other and form the above condensed ring of binary, R on its skeleton
2Be selected from C
1～C
18Alkyl or perfluoroalkyl, C
6～C
24Aralkyl or alkaryl, X is a halogen, n is 1～3 integer.
As carrier, load contains the semi-metallocene active ingredient of beta-diketo derivative part with Magnesium Chloride Anhydrous activation back in the present invention, and the catalyzer that makes carries titanium amount height, and has good mobility and intensity.This catalyzer is used for ethylene polymerization, has catalytic activity preferably, and the resulting polymers particle form is good, has higher bulk density.
Embodiment
The inventive method is suspended in Magnesium Chloride Anhydrous in the unreactive hydrocarbons solvent, with Ti (OR)
4Contact reacts activates with ROH again, makes the magnesium dichloride-alcohol carrier, and then with aluminum alkyls the magnesium dichloride-alcohol carrier is handled, and the described semi-metallocene active ingredient of load type (I) is made load type non-metallocene catalyst again.Therefore the pure consumption of activation Magnesium Chloride Anhydrous is few in the inventive method, so magnesium chloride is in solid-stately in treating processes all the time, can make activation back carrier have good form, and the supported catalyst that makes also has particle form preferably.In addition, because year titanium amount of the feed ratio of semi-metallocene active ingredient and carrier and loaded catalyst is directly proportional, thereby the supported catalyst that makes carries titanium amount height, makes the unit mass activity of such catalysts obviously improve.
Substituting group in the semi-metallocene active ingredient of the described formula of the inventive method (I) in R and the R ' difference beta-diketonate ligand, R and the preferred C of R ' difference
1～C
3Alkyl, C
1～C
3Perfluoroalkyl or C
6～C
9Alkaryl, more preferably methyl or phenyl.Cp ' has 1～5 substituent R for containing the ligand groups of cyclopentadienyl skeleton on the cyclopentadienyl skeleton
2Suitable Cp ' is for cyclopentadiene or contain substituent cyclopentadienyl, preferred cyclopentadienyl, C
1～C
4The alkyl list replaces or polysubstituted cyclopentadienyl, fluorenyl or indenyl, as methyl cyclopentadienyl, butyl cyclopentadienyl, 1-butyl-3-methyl cyclopentadienyl or pentamethyl-cyclopentadienyl, more preferably cyclopentadienyl, fluorenyl or indenyl.The preferred chlorine of X.
The compound of comparatively preferred formula (I) has: cyclopentadiene-(methyl ethyl diketone)-titanium dichloride, cyclopentadiene-two (methyl ethyl diketone)-titanium chloride, cyclopentadiene-tri acetylacetonato titanium, cyclopentadiene-(diphenylpropane-1,3-dione(DPPO))-titanium dichloride, cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO))-titanium chloride, cyclopentadiene-three (diphenylpropane-1,3-dione(DPPO)) titanium, methyl cyclopentadiene-(methyl ethyl diketone)-titanium dichloride, methyl cyclopentadiene-two (methyl ethyl diketone)-titanium chloride, methyl cyclopentadiene-tri acetylacetonato titanium, methyl cyclopentadiene-(diphenylpropane-1,3-dione(DPPO))-titanium dichloride, methyl cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO))-titanium chloride, methyl cyclopentadiene-three (diphenylpropane-1,3-dione(DPPO)) titanium, butyl cyclopentadiene-(methyl ethyl diketone)-titanium dichloride, butyl cyclopentadiene-two (methyl ethyl diketone)-titanium chloride, butyl cyclopentadiene-tri acetylacetonato titanium, butyl cyclopentadiene-(diphenylpropane-1,3-dione(DPPO))-titanium dichloride, butyl cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO))-titanium chloride, butyl cyclopentadiene-three (diphenylpropane-1,3-dione(DPPO)) titanium, pentamethyl-cyclopentadiene-(methyl ethyl diketone)-titanium dichloride, pentamethyl-cyclopentadiene-two (methyl ethyl diketone)-titanium chloride, pentamethyl-cyclopentadiene-tri acetylacetonato titanium, pentamethyl-cyclopentadiene-(diphenylpropane-1,3-dione(DPPO))-titanium dichloride, pentamethyl-cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO))-titanium chloride, pentamethyl-cyclopentadiene-three (diphenylpropane-1,3-dione(DPPO)) titanium, cyclopentadiene-(trifluoroacetylacetone) titanium dichloride, cyclopentadiene-two (trifluoroacetylacetone) titanium chloride, cyclopentadiene-three (trifluoroacetylacetone) titanium, methyl cyclopentadiene-(trifluoroacetylacetone) titanium dichloride, methyl cyclopentadiene-two (trifluoroacetylacetone) titanium chloride, methyl cyclopentadiene-three (trifluoroacetylacetone) titanium, indenyl-(methyl ethyl diketone)-titanium dichloride, indenyl-two (methyl ethyl diketone)-titanium chloride, indenyl-tri acetylacetonato titanium, indenyl-(diphenylpropane-1,3-dione(DPPO))-titanium dichloride, indenyl-two (diphenylpropane-1,3-dione(DPPO))-titanium chloride, indenyl-three (diphenylpropane-1,3-dione(DPPO)) titanium.
The inventive method (1) step is the activation treatment step of anhydrous chlorides of rase magnesium carrier, Magnesium Chloride Anhydrous is suspended in the unreactive hydrocarbons, with Ti (OR
1)
4With the alcohol reaction, be preferably elder generation's adding Ti (OR in Magnesium Chloride Anhydrous suspension
1)
4React, add alcohol again and react.Described Ti (OR
1)
4Preferred ethanolato-titanium, titanium propanolate or titanium butoxide, described Ti (OR
1)
4With the mol ratio of Magnesium Chloride Anhydrous preferred 0.01～0.1.
The preferred C of the described unreactive hydrocarbons solvent of the inventive method
5～C
10Alkane, more preferably hexane, decane, heptane or octane.The suitable mass ratio of unreactive hydrocarbons solvent and Magnesium Chloride Anhydrous is 5～100, preferred 5～20.Described Fatty Alcohol(C12-C14 and C12-C18) preferred alcohol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, enanthol, octanol or isooctyl alcohol.
The inventive method (2) step is with aluminum alkyls carrier to be handled, preferred triethyl aluminum of described aluminum alkyls or triisobutyl aluminium, the mol ratio of aluminum alkyls and magnesium chloride preferred 0.1～1.0.The temperature of carrier being handled with aluminum alkyls is-20～20 ℃, preferred-10～10 ℃.
Described (3) step is the loaded by semi-metallocene active ingredient, and described polar organic solvent is selected from C
1～C
5Chloroparaffin, as methylene dichloride, trichloromethane, ethylene dichloride or tetracol phenixin.The temperature of reaction of carrier and semi-metallocene active ingredient is 30～200 ℃, preferred 50～100 ℃.In the loading process, add the semi-metallocene active ingredient amount should to make the mol ratio of magnesium chloride and semi-metallocene active ingredient be 1～20, preferred 1～10.
Titanium content is 3.0～10 quality % in the catalyzer of the inventive method preparation, preferred 4.0～8.0 quality %, more preferably 5.1～8.0 quality %, Mg content is 2.5～20.0 quality %, preferred 5.0～15.0 quality %, aluminium content are 0.5～3.0 quality %, preferred 0.8～2.0 quality %.
The described Magnesium Chloride Anhydrous of the inventive method, its water content should be less than 1.0 quality %, and average particle size is 30～40 microns, and specific surface area is 10～20 meters
2/ gram.
The preparation method of described formula (I) semi-metallocene active ingredient is: in the presence of ether, make TiX
4With general formula be R '-C (O)-CH
2The beta-diketone compound of-C (O)-R reacts under reflux temperature by 1: 1～3 mol ratio, removes and desolvates, and obtains the beta diketone titanium compound.Then at organic solvent, as toluene exist make down an alkali metal salt Cp ' M of containing the cyclopentadienyl skeleton compound and beta diketone titanium compound by etc. molar ratio reaction, method is the beta diketone titanium compound to be dissolved in toluene earlier be mixed with solution preferably, and then add Cp ' M, and react at-15～25 ℃, remove and desolvate, the most handy ether washing of gained solid matter, or as required the solid matter recrystallization is purified, the recrystallization solvent for use is a polar organic solvent, as halogenated alkane.M among described Cp ' M is a basic metal, preferred sodium.The more detailed preparation method of described semi-metallocene active ingredient is referring to CN1295088A.
The loaded catalyst of the present invention preparation is applicable to the copolymerization of ethylene homo or ethene and alpha-olefin, also needs to add aikyiaiurnirsoxan beta during polymerization or aluminum alkyls is a promotor, and polymerization temperature is 10～100 ℃, preferred 30～80 ℃.Polymerization can adopt body, slurry or technology such as gas-phase fluidized-bed to carry out.The mol ratio of titanium in aluminium and the Primary Catalysts in promotor during polyreaction, promptly the Al/Ti mol ratio is 25～2000, preferred 100～1500.
Described aikyiaiurnirsoxan beta can be linear or cyclic, preferable methyl aikyiaiurnirsoxan beta, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide, the preferred triethyl aluminum of described aluminum alkyls, triisobutyl aluminium, three hexyl aluminium or their mixture.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare loaded catalyst with the inventive method.
(1) preparation cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride
With concentration is the TiCl of 4.74 quality %
4Diethyl ether solution, the diethyl ether solution of the diphenylpropane-1,3-dione(DPPO) of 56.06 quality % (production of Shanghai chemical reagent work) adds in the encloses container, and makes TiCl
4With the mol ratio of diphenylpropane-1,3-dione(DPPO) be 1: 1, be heated with stirring to reflux temperature, reacted 1 hour, filter, solid makes (diphenylpropane-1,3-dione(DPPO)) titanous chloride with ether washing 3 times.
Get 5.5 milliliters of cyclopentadiene and be dissolved in 25 milliliters of tetrahydrofuran (THF)s ,-10 ℃ add 1.4 gram sodium Metal 99.5 reactions 2 hours, and removal of solvent under reduced pressure obtains 4.67 gram cyclopentadiene sodium.
(diphenylpropane-1,3-dione(DPPO)) titanous chloride is dissolved in the solution that toluene is made into 94.35 quality %, adding concentration at-10 ℃ then is the toluene solution of the cyclopentadiene sodium of 22.02 quality %, and the mol ratio that makes (diphenylpropane-1,3-dione(DPPO)) titanous chloride and cyclopentadiene sodium is 1: 1,20 ℃ of stirring reactions 5 hours, filter, wash 3 times with ether, 50 ℃ of dryings 24 hours make cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(2) preparation loaded catalyst
(a) get 40 milliliters of exsiccant hexanes, the there-necked flask that places nitrogen purging to cross stirs 0.30 milliliter (8.8 * 10 of adding down
-4Mol) titanium n-butoxide adds Magnesium Chloride Anhydrous (production of Jinzhou aluminium manufacturer) 2.0 grams (2.1 * 10 then
-2Mol), it is suspended in the hexane, is heated to 70 ℃, under this temperature, stirred 30 minutes, drip propyl carbinol again 0.8 milliliter (8.7 * 10
-3Mol), stirred suspension 30 minutes filters, and solid is with 30 milliliters of hexane wash three times, and 30 ℃ of dryings 2 hours must mobile good white powder carrier a.
(b) there-necked flask that places nitrogen purging to cross carrier a, add 40 milliliters of exsiccant hexanes, stirring down, adding 6.4 ml concns are the hexane solution of the triethyl aluminum of 1 mol, 0 ℃ was reacted 2 hours, filter, solid is with 30 milliliters of hexane wash three times, and 30 ℃ of dryings 2 hours obtain the carrier b that aluminum alkyls is handled.
(c) there-necked flask that places nitrogen purging to cross carrier b adds 40 milliliters of exsiccant hexanes, will contain 2.8 grams (6.88 * 10
-3Mol) dichloromethane solution of cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride splashes into wherein for 30 milliliters, be heated to 70 ℃ of stirring reactions 1 hour, and filtered, solid is with 30 milliliters of hexane wash three times, 30 ℃ of dryings 2 hours obtain mobile well deep yellow powder catalyst A.The titanium content that plasma emission spectrum (ICP) method records catalyst A is 5.34 quality %, and Mg content is 10.84 quality %, and aluminium content is 1.23 quality %.
Example 2
Method by example 1 prepares supported catalyst B, and different is to add 40 milliliters in (c) step to contain 3.7 grams (9.10 * 10
-3Mol) dichloromethane solution of cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride, the titanium content of the catalyst B that obtains is 6.23 quality %, and Mg content is 9.12 quality %, and aluminium content is 1.01 quality %.
Example 3
Method by example 1 prepares supported catalyst C, and different is to add 45 milliliters in (c) step to contain 4.4 grams (1.08 * 10
-2Mol) dichloromethane solution of cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride, the titanium content of the catalyzer C that obtains is 7.08 quality %, and Mg content is 8.62 quality %, and aluminium content is 0.92 quality %.
Example 4
Method by example 1 prepares supported catalyst D, and the amount of the propyl carbinol that adds in different is (a) step is 1.2 milliliter (1.3 * 10
-2Mol), (b) adding 8.7 ml concns in the step is the hexane solution of the triethyl aluminum of 1 mol, and the titanium content of the catalyzer D that obtains is 5.45 quality %, and Mg content is 10.24 quality %, and aluminium content is 1.35 quality %.
Example 5
Method by example 1 prepares supported catalyst E, and different is that the propyl carbinol that adds in (a) step is 0.4 milliliter (4.3 * 10
-3Mol), (b) adding 3.6 ml concns in the step is the hexane solution of the triethyl aluminum of 1 mol, and the titanium content of the catalyzer E that obtains is 3.5 quality %, and Mg content is 13.13 quality %, and aluminium content is 1.02 quality %.
Example 6
Method by example 1 prepares supported catalyst F, and different is that the propyl carbinol that adds in (a) step is 1.6 milliliter (1.7 * 10
-2Mol), (b) adding 10.5 ml concns in the step is the hexane solution of the triethyl aluminum of 1 mol, and the titanium content of the catalyzer F that makes is 4.5 quality %, and Mg content is 11.19 quality %, and aluminium content is 1.64 quality %.
Example 7
Method by example 1 prepares supported catalyst G, and different is to add 0.5 milliliter (8.7 * 10 in (a) step
-3Mol) ethanol, (b) adding 7.4 ml concns in the step is the hexane solution of the triethyl aluminum of 1 mol, and the titanium content of the catalyzer G that makes is 4.66 quality %, and Mg content is 11.32 quality %, and aluminium content is 1.14 quality %.
Example 8
Method by example 1 prepares supported catalyst H, and different is to add 1.5 milliliter (8.7 * 10 in (a) step
-3Mol) isooctyl alcohol, (b) adding 5.4 ml concns in the step is the hexane solution of the triethyl aluminum of 1 mol, and the titanium content of the catalyzer H that makes is 3.5 quality %, and Mg content is 12.93 quality %, and aluminium content is 1.03 quality %.
Example 9
Method by example 1 prepares supported catalyst I, different is that adding 5.4 ml concns are the hexane solution of the triisobutyl aluminium of 1 mol in (b) step, the titanium content of the catalyst I that makes is 5.28 quality %, and Mg content is 10.94 quality %, and aluminium content is 1.27 quality %.
Example 10
(1) preparation cyclopentadiene-(methyl ethyl diketone) titanium dichloride
With concentration is the TiCl of 4.47 quality %
4Diethyl ether solution, concentration are that the diethyl ether solution of 2.51 quality % methyl ethyl diketones adds in the closed reactor, and make TiCl
4With the mol ratio of methyl ethyl diketone be 1: 1, be heated with stirring to reflux temperature, reacted 1 hour, cross and to filter out ether, solid makes (methyl ethyl diketone) titanous chloride with ether washing 3 times.
Above-mentioned (methyl ethyl diketone) titanous chloride is dissolved in the solution that toluene is made 63.37 quality %, adding concentration at-10 ℃ is the toluene solution of the cyclopentadiene sodium of 22.0 quality %, and to make the mol ratio of cyclopentadiene sodium and (methyl ethyl diketone) titanous chloride be 1: 1,20 ℃ of stirring reactions 5 hours, remove by filter toluene, solid washs 3 times with ether, use 30 milliliters of methylene dichloride dissolved solidss again, remove by filter insolubles, filtrate is concentrated into dried, 50 ℃ of dryings obtained cyclopentadiene-(methyl ethyl diketone)-titanium dichloride in 4 hours.
(2) preparation loaded catalyst
Prepare supported catalyst J by example 1 (2) one step process, different is to add in (c) step to contain 1.8 grams (6.34 * 10
-3Mol) dichloromethane solution of cyclopentadiene-(methyl ethyl diketone) titanium dichloride is 30 milliliters, and the titanium content of the catalyzer J that makes is 5.62 quality %, and Mg content is 10.76 quality %, and aluminium content is 1.21 quality %.
Comparative Examples 1
Prepare catalyzer M according to the CN00124667 method.Get water content and put into reaction flask less than dry magnesium chloride 1.2 grams of 1.0 quality %, add 60 milliliters of exsiccant tetrahydrofuran (THF)s, 55 ℃ of reactions formed adduct solution in 1 hour.Slowly splash into 15 milliliters of dichloromethane solutions that are dissolved with 0.51 gram cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride in the reaction flask, 20 ℃ of stirring reactions 1 hour, stop to stir, add 100 milliliters of hexane solutions, staticly settled 2 hours, filter, solid was obtained 1.01 gram pink colour catalyzer M in 6 hours 20 ℃ of dryings.The titanium content of catalyzer M is 1.11 quality %, and Mg content is 13.36 quality %.
Example 11～21
Following example carries out the reaction of normal pressure ethylene homo.
250 milliliters of round-bottomed flasks are vacuumized back nitrogen purging three times, feed ethene behind the emptying nitrogen, keep-up pressure and be 0.1MPa, add toluene solution, the 50 milliliters of exsiccant hexanes of the methylaluminoxane that 9.6 ml concns are 10 quality % (MAO) and contain the catalyzer of 0.03mmolTi, 40 ℃ of polyreactions 0.5 hour are used the HCl termination reaction.The Al/Ti mol ratio is 500 during polymerization.Each example catalyst system therefor, catalytic activity and polymer property see Table 1.
Example 22～32
Following example carries out the high-pressure ethylene homopolymerization.
2 liters of stainless steel autoclaves are vacuumized back nitrogen purging three times, feed ethene behind the emptying nitrogen, keep-up pressure and be 0.8MPa, the catalyzer that adds hexane solution that 20 ml concns are the triethyl aluminum of 10 quality %, 1 liter of exsiccant hexane and 0.1mmolTi, 70 ℃ of polyreactions 2 hours, use the HCl termination reaction, the Al/Ti mol ratio is 200 during polymerization.Each example catalyst system therefor, catalytic activity and polymer property see Table 2.
By table 1 and table 2 data as can be known, the catalyzer of the inventive method preparation has the higher titanium amount of carrying than comparative catalyst M, and therefore, the catalyst activity of unit mass is higher, has higher actual application value.
Table 1
Table 2
Claims (9)
1, a kind of preparation method of polyethylene catalysts of loaded by semi-metallocene comprises the steps:
(1) Magnesium Chloride Anhydrous is suspended in the unreactive hydrocarbons solvent, in 30～200 ℃ and Ti (OR
1)
4And C
2～C
8The abundant contact reacts of Fatty Alcohol(C12-C14 and C12-C18), then solid drying is obtained carrier, described Ti (OR
1)
4With the mol ratio of Magnesium Chloride Anhydrous be 0.01～0.2, Fatty Alcohol(C12-C14 and C12-C18) and Magnesium Chloride Anhydrous mol ratio are 0.1～1.0, formula Ti (OR
1)
4In R
1Be selected from C
1～C
7Alkyl;
(2) (1) step described dry back carrier is handled after drying with aluminum alkyls at-20～20 ℃ in the presence of unreactive hydrocarbons solvent, the mol ratio of aluminum alkyls and magnesium chloride is 0.1～2.0;
(3) in the presence of polar organic solvent, the magnesium chloride support that will obtain after will handling with aluminum alkyls with have the semi-metallocene active ingredient of formula (I) expression formula 30～200 ℃ of abundant contact reactss, collect the solids after drying, the mol ratio of magnesium chloride and semi-metallocene active ingredient is 1～20
In the formula (I), R is identical with R ' or inequality, is C
1～C
12Alkyl, C
6～C
9Alkaryl or C
1～C
12Perfluoroalkyl, Cp ' has 1～5 substituent R for containing the ligand groups of cyclopentadienyl skeleton on the cyclopentadienyl skeleton
2, two adjacent substituting groups can be connected with each other and form the above condensed ring of binary, R on its skeleton
2Be selected from C
1～C
18Alkyl or perfluoroalkyl, C
6～C
24Aralkyl or alkaryl, X is a halogen, n is 1～3 integer,
Titanium content is 3.0～10 quality % in the described catalyzer, and Mg content is 2.5～20.0 quality %, and aluminium content is 0.5～3.0 quality %.
2, in accordance with the method for claim 1, it is characterized in that middle R of described formula (I) and R ' are respectively C
1～C
3Alkyl, C
1～C
3Perfluoroalkyl or C
6～C
9Alkaryl, Cp ' is cyclopentadienyl, C
1～C
4The alkyl list replaces or polysubstituted cyclopentadienyl, fluorenyl or indenyl.
3, in accordance with the method for claim 1, it is characterized in that middle R of described formula (I) and R ' are respectively C
1～C
3Alkyl or C
6～C
9Alkaryl, Cp ' is cyclopentadienyl, fluorenyl or indenyl, X is a chlorine.
4, in accordance with the method for claim 1, it is characterized in that the Ti (OR described in (1) step
1)
4Be four titanium butoxide or purity titanium tetraethoxide, described Ti (OR
1)
4With the mol ratio of Magnesium Chloride Anhydrous be 0.01～0.1.
5,, it is characterized in that described unreactive hydrocarbons solvent is C according to claim 1 or 4 described methods
5～C
10Alkane, described Fatty Alcohol(C12-C14 and C12-C18) is ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, enanthol, octanol or isooctyl alcohol.
6, in accordance with the method for claim 1, it is characterized in that described aluminum alkyls of (2) step is triethyl aluminum or triisobutyl aluminium, the mol ratio of described aluminum alkyls and magnesium chloride is 0.1～1.0.
7, in accordance with the method for claim 1, it is characterized in that described polar organic solvent is selected from C
1～C
5Chloroparaffin.
8, in accordance with the method for claim 7, it is characterized in that described chloroparaffin is methylene dichloride, trichloromethane, ethylene dichloride or tetracol phenixin.
9, in accordance with the method for claim 1, it is characterized in that the mol ratio of magnesium chloride and semi-metallocene active ingredient is 1～10 in the carrier.
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