CN1156496C - Polythene catalyst loaded by double-carrier of magnesium chloride/kaolin and its preparation method - Google Patents
Polythene catalyst loaded by double-carrier of magnesium chloride/kaolin and its preparation method Download PDFInfo
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- CN1156496C CN1156496C CNB011237589A CN01123758A CN1156496C CN 1156496 C CN1156496 C CN 1156496C CN B011237589 A CNB011237589 A CN B011237589A CN 01123758 A CN01123758 A CN 01123758A CN 1156496 C CN1156496 C CN 1156496C
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Abstract
The present invention relates to a polythene catalyst for loading semimetallocene, which comprises a double carrier of magnesium halide/kaolin and an active component of semimetallocene having the expression formula (I). In the formula (I), R and R' can be identical or different and represent C1 to C12 alkyl, C6 to C9 alkaryl or C1 to C12 perfluoroalkyl; Cp' is a ligand group comprising a cyclopentadiene framework, the cyclopentadiene framework has 1 to 5 substitutents R1, and two adjacent substitutents on the framework can be mutually connected to form a condensed ring of more than two dimensions; R1 is selected from hydrogen, C1 to C18 alkyl or perfluoroalkyl, and C6 to C24 aralkyl or alkaryl; X is halogen, and n is an integer from 1 to 3.
Description
Technical field
The present invention is a kind of loading type semi-metallocene catalyst and preparation method.Specifically, be ethylene rolymerization catalyst and the preparation method that a kind of load contains the semi-metallocene active ingredient of beta-diketo derivative part.
Background technology
Continuing typical is the transistion metal compound of part with cyclopentadiene and derivative thereof, be after the metallocene catalyst, the class metallocene compound that contains coordination heteroatom ligands such as aerobic, nitrogen in the another kind of conjugated system causes more and more that in the application aspect polyolefine, the especially polyethylene catalysts people pay attention to and pay close attention to.
The class metallocene 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.The preferred Primary Catalysts of this patent 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.
Recently, people also make loaded catalyst as active constituent loading with above-mentioned catalyzer in research on different mineral compound carriers in research metallocene and class metallocene catalyst.As, it is active ingredient with the metallocene that USP5869417 discloses a kind of, molecular sieve is the preparation method of the loaded catalyst of carrier, the used carrier of this patent is the macroporous structure molecular sieve with 7～15 apertures, 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.
Though with Magnesium Chloride Anhydrous is that carrier loaded metallocene or class metallocene catalyst can show advantages of high catalytic activity in olefin polymerization process, but this type of catalyzer is highly brittle, broken easily in polymerization reactor, thus cause polymer morphology bad, be unfavorable in gas fluidised bed polymerisation, using.Therefore, people consider silica gel and magnesium chloride are made two carriers, strengthen the flowability and the intensity of carrier.Reported as EP0878485A1 and to have used MgCl
2/ SiO
2Two carrier loaded metallocene catalysts can be used for ethene gas phase and slurry polymerization catalysis, have good catalytic activity.Silica gel mainly plays dissemination in two carriers, and makes the catalyzer of preparing have the granularity of good intensity, flowability and certain size.But the price of silica gel is more expensive, therefore, seek a kind of cheapness and can with the essentially identical carrier of silica gel performance, become the developing direction that people prepare catalyzer.
Summary of the invention
The purpose of this invention is to provide two carrier loaded semi-metallocene polyethylene catalysts of a kind of magnesium halide/kaolin and preparation method thereof.
We find, what will be used to prepare syndiotactic polystyrene is the catalyzer that half luxuriant titanium active constituent loading of part makes in the two carriers of magnesium halide/kaolin with the beta-diketo derivative, be used for ethylene polymerization, have catalytic activity and copolymerization performance preferably, wherein kaolinic use has not only reduced the cost of catalyzer
Also make catalyzer have good mobility and intensity.Cooperate with the methylaluminoxane promotor as catalyzer to be used for ethylene homo and to react with the present invention preparation, polymerization under 0.8MPa, 70 ℃ of conditions, its activity can reach 8.65 * 10
6Gram polyethylene/mole titanium hour.
Embodiment
Catalyzer provided by the invention comprises two carriers of magnesium halide/kaolin and the semi-metallocene active ingredient with formula (I) expression formula, and the titanium content in the described catalyzer is 0.1～10 heavy %, and Mg content is 2.5～20.0 heavy %,
R can be identical or inequality with R ' in the formula (I), 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
1, two adjacent substituting groups on its skeleton can be connected with each other and form the above condensed ring of binary, preferred chlorine, R
1Be selected from hydrogen, C
1～C
18Alkyl or perfluoroalkyl, C
6～C
24Aralkyl or alkaryl, X is a halogen, n is 1～3 integer.
The preferred C of R and R ' in the semi-metallocene active ingredient of formula (I)
1～C
3Alkyl, C
1～C
3Perfluoroalkyl or C
6～C
9Alkaryl, methyl or phenyl more preferably; The preferred cyclopentadienyl of Cp ', fluorenyl, indenyl, or C
1～C
4The alkyl list replaces or polysubstituted above-mentioned group, as methyl cyclopentadienyl, butyl cyclopentadienyl, 1-butyl-3-methyl cyclopentadienyl or pentamethyl-cyclopentadienyl.
Comparatively preferred formula (I) compound 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 preferred magnesium chloride of described magnesium halide, preferred 0.5～5.0 heavy % of the titanium content in the catalyzer, Mg content preferred 5.0～15.0 heavy %.
Preparation of catalysts method provided by the invention comprises anhydrous magnesium halide is dissolved in the tetrahydrofuran-ethyl alcohol mixed solvent, again with the abundant contact reacts of kaolin, thereafter adding unreactive hydrocarbons solvent is placed to precipitation and fully separates out, filtration, drying make carrier, this carrier is handled the back with the toluene solution of methylaluminoxane fully to be contacted with the semi-metallocene active ingredient that is dissolved in polar organic solvent, add unreactive hydrocarbons solvent to precipitation and fully separate out, then filtration, drying.
The preferred magnesium chloride of the described magnesium halide of aforesaid method, its water content should be less than 1.0 heavy %, and average particle size is 30～40 microns, and specific surface area is 10～20 meters
2/ gram.
Described kaolinic specific surface is 16～20 meters
2/ gram, pore volume are 0.11～0.14 milliliter/gram, and average particle size is 30～50 microns.Need before using at 200～550 ℃, preferred 300～500 ℃ of activation 4～8 hours are to remove its moisture and part surface hydroxyl.
In the catalyst preparation process of the present invention, need two carrier, loaded by semi-metallocene active ingredients again of preparation magnesium halide/kaolin earlier.The preparation of two carriers is with the tetrahydrofuran-ethyl alcohol mixed solvent anhydrous magnesium halide to be dissolved, and forms adduct solution, and then fully reacts with activatory kaolin.During obtain solution, the consumption of tetrahydrofuran-ethyl alcohol is 10～250 times of anhydrous magnesium halide weight.Tetrahydrofuran (THF) and alcoholic acid volume ratio are 5～50: 1 in the tetrahydrofuran-ethyl alcohol mixed solvent, are preferably 2～25: 1, and preferred 10: 1, the temperature of dissolving magnesium halide was 20～80 ℃, preferred 40～60 ℃.Adduct of magnesium halides solution and kaolinic temperature of reaction are 30～70 ℃, and preferred 30～55 ℃, the time is 0.5～10 hour, and preferred 0.5～2.0 hour, magnesium halide and kaolinic weight ratio were 10～0.5, preferred 5～2: 1.
Above-mentioned and the reacted magnesium halide of kaolin make two carriers through precipitation, filtration, drying.This carrier also needs fully to contact with the toluene solution of methylaluminoxane, its temperature is 10～50 ℃, it is 0.1～500: 1 that the methylaluminoxane that is used to handle and the mol ratio of magnesium halide are calculated with the Al/Mg mol ratio, filter then, drying, this carrier is fully contacted with the semi-metallocene active ingredient that is dissolved in polar organic solvent, 10～70 ℃ were reacted 5～24 hours again, and preferred temperature of reaction is 10～30 ℃, time is 0.5～2.0 hour, through precipitating, filter, be drying to obtain catalyzer of the present invention.The mol ratio of magnesium halide and semi-metallocene is 5～500: 1 in the reaction process, preferred 5～50: 1.
When handling carrier and loaded by semi-metallocene active ingredient with methylaluminoxane, preferably carrier is used with reactant and all nonreactive inert material of resultant be that dispersion agent disperses, preferred dispersing agent is toluene or methylene dichloride, and suitable dispersant dosage should be 0.5～10 times of vehicle weight.
The described polar organic solvent that is used to dissolve the semi-metallocene active ingredient is selected from C
1～C
5Halogenated alkane, preferred C
1～C
3Chloroparaffin, chloroparaffin is methylene dichloride, trichloromethane, ethylene dichloride, tetracol phenixin preferably, its consumption is 5～200 times of semi-metallocene active ingredient weight.
The described unreactive hydrocarbons solvent that is used for the precipitin reaction thing is selected from C
5～C
20Alkane, preferred C
5～C
7Alkane, as hexane, heptane.
Preferred 30～50 ℃ of drying temperature described in the aforesaid method, preferred 3～6 hours of time.
The preparation method of the semi-metallocene active ingredient of described formula (I) is: make TiX in the presence of ether
4And have R '-C (O)-CH that general formula is
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, better method is the beta diketone titanium compound to be dissolved in toluene earlier be mixed with solution, 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.
Loaded catalyst provided by the invention is applicable to the homopolymerization of ethene or the copolymerization of ethene and alpha-olefin, also needs to add aikyiaiurnirsoxan beta during polymerization or aluminum alkyls is a promotor, and polymerization temperature is 10～100 ℃, is preferably 30～80 ℃.Preferred comonomer is C
3～C
15Alpha-olefin, as butylene, amylene, hexene or vinylbenzene.Polymerization can adopt body, slurry, technology such as gas-phase fluidized-bed to carry out.
Described promotor aikyiaiurnirsoxan beta can be linear or cyclic, preferable methyl aikyiaiurnirsoxan beta, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide.The preferred triethyl aluminum of promotor aluminum alkyls, triisobutyl aluminium, three hexyl aluminium or their mixture.
The mol ratio of titanium in aluminium and the Primary Catalysts in promotor during polyreaction, promptly the Al/Ti ratio is 25～2000, preferred 800～1500.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
The preparation active ingredient is the supported catalyst of cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(1) preparation cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride
A. with concentration the TiCl of 4.74 heavy %
4Diethyl ether solution, the diethyl ether solution of the diphenylpropane-1,3-dione(DPPO) (Shanghai chemical reagent work) of 56.06 heavy % 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.
B. 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.
C. (diphenylpropane-1,3-dione(DPPO)) titanous chloride is dissolved in the solution that toluene is made into 94.35 heavy %, add the toluene solution that concentration is the cyclopentadiene sodium of 22.02 heavy % at-10 ℃ then, 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 2 hours make cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(2) preparation supported catalyst
A) getting granularity that Lanzhou Petrochemical Company produces is that 30～50 microns kaolin carried out activation treatment in 6 hours 500 ℃ of roastings.
B) get 3 grams and get water content and put into reaction flask less than the dry magnesium chlorides (productions of Jinzhou aluminium manufacturer) of 1.0 heavy %, adds 50 milliliters of exsiccant tetrahydrofuran (THF)s and 5 milliliters of exsiccant ethanol, 55 ℃ are reacted 1 hour formation adduct solution down.Be chilled to room temperature then, slowly add 1.5 gram activation back kaolin, 50 ℃ of following stirring reactions 2 hours, stop to stir after being cooled to room temperature, add 100 milliliters of hexanes, leave standstill extremely to precipitate in 5 hours and fully separate out after-filtration, solid was obtained 7.1 gram carriers in 6 hours 20 ℃ of dryings.
The above-mentioned two carriers that prepare are disperseed with 20 milliliters of toluene, add 3 milliliters of (MAO) toluene solutions (production of Albemarle company) that contain the methylaluminoxane of aluminium 10 heavy %, stirring at room 5 hours is filtered, solid is with 30 milliliters of toluene wash three times, 20 ℃ of dryings 10 hours.
C) above-mentioned two carriers of handling with MAO are disperseed with 20 milliliters of toluene, slowly splash into 20 milliliters of dichloromethane solutions that are dissolved with 1.0 gram cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride, 8 hours after-filtration of 20 ℃ of stirring reactions, solid obtains the catalyst A of 4.75 gram deep yellows 20 ℃ of dryings 6 hours.The titanium content that plasma emission spectrum (ICP) method records catalyst A is 1.98 heavy %, and Mg content is 14.9 heavy %.
Example 2
The preparation active ingredient is the supported catalyst of butyl cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(1) preparation butyl cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride
Method by (1) step of example 1 prepares butyl cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.Different is that b replaces cyclopentadiene to make butyl cyclopentadiene sodium with the butyl cyclopentadiene in the step, in c step, be that the toluene solution of toluene solution and (diphenylpropane-1,3-dione(DPPO)) titanous chloride of the butyl cyclopentadiene sodium of 23.73 heavy % reacts then with concentration, filtration, washing, drying make butyl cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(2) preparation supported catalyst
Method by (2) step of example 1 prepares supported catalyst, that different is c) react with 20 milliliters of dichloromethane solution and two carriers of magnesium chloride/kaolin that are dissolved with 2 gram indenyl rings pentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride in the step, obtain the filbert catalyst B of 4.9 grams.The titanium content of catalyst B is 1.56 heavy %, and Mg content is 7.5 heavy %.
Example 3
The preparation active ingredient is the supported catalyst of indenyl-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(1) preparation indenyl-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride
Method by (1) step of example 1 prepares indenyl rings pentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.Different is that b replaces cyclopentadiene to make indenyl sodium with indenes in the step, in c step, be that the toluene solution of toluene solution and (diphenylpropane-1,3-dione(DPPO)) titanous chloride of the indenyl sodium of 24.67 heavy % reacts then with concentration, filtration, washing, drying make indenyl-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(2) preparation supported catalyst
Method by (2) step of example 1 prepares supported catalyst, and that different is c) go on foot the dichloromethane solution and the two carriers reactions of magnesium chloride/kaolin that are dissolved with 2.5 gram indenyl-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride with 20 milliliters, obtain the filbert catalyzer C of 5.2 grams.The titanium content of catalyzer C is that 1.49 heavy %, Mg content are 7.1 heavy %.
Example 4
The preparation active ingredient is the supported catalyst of cyclopentadiene-(methyl ethyl diketone) titanium dichloride.
(1) preparation cyclopentadiene-(methyl ethyl diketone) titanium dichloride
A. with concentration the TiCl of 4.47 heavy %
4Diethyl ether solution, concentration are that the diethyl ether solution of 2.51 heavy % 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.
B. above-mentioned (methyl ethyl diketone) titanous chloride is dissolved in toluene and makes the solution of 63.37 heavy %, add the toluene solution that concentration is the cyclopentadiene sodium of 22.0 heavy % at-10 ℃, and to make the mol ratio of cyclopentadiene sodium and (methyl ethyl diketone) titanous chloride be 1: 1,20 ℃ of following 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 supported catalyst
Method by (2) step of example 1 prepares supported catalyst, and that different is c) go on foot the chloroform soln and the two carriers reactions of magnesium chloride/kaolin that are dissolved with 1.8 gram cyclopentadiene-(methyl ethyl diketone)-titanium dichloride with 20 milliliters, obtain the filbert catalyzer D of 4.9 grams.The titanium content of catalyzer D is that 1.72 heavy %, Mg content are 7.5 heavy %.
Example 5
The preparation active ingredient is the supported catalyst of butyl cyclopentadiene-(methyl ethyl diketone)-titanium dichloride.
(1) preparation butyl cyclopentadiene-(methyl ethyl diketone)-titanium dichloride
Method by example 4 prepares active ingredient, and different is to react with butyl cyclopentadiene sodium and (methyl ethyl diketone) titanous chloride in the b step, makes butyl cyclopentadiene-(methyl ethyl diketone)-titanium dichloride.
(2) preparation supported catalyst
Method by (2) step of example 1 prepares supported catalyst, that different is c) go on foot the dichloromethane solution and the two carriers reactions of magnesium chloride/kaolin that are dissolved with 1.9 gram butyl cyclopentadiene-(methyl ethyl diketone)-titanium dichloride with 20 milliliters, obtain the filbert catalyzer E of 4.7 grams.The titanium content of catalyzer E is that 1.43 heavy %, Mg content are 7.8 heavy %.
Example 6
The preparation active ingredient is the supported catalyst of indenyl-(methyl ethyl diketone)-titanium dichloride.
(1) preparation indenyl-(methyl ethyl diketone)-titanium dichloride
Press the method preparation component of giving birth to alive of example 4, different is with indenyl rings pentadiene sodium and the reaction of (methyl ethyl diketone) titanous chloride, makes active ingredient indenyl-(methyl ethyl diketone)-titanium dichloride.
(2) preparation supported catalyst
Method by (2) step of example 1 prepares supported catalyst, and that different is c) go on foot the dichloromethane solution and the two carriers reactions of magnesium chloride/kaolin that are dissolved with 2.3 gram indenyl-(methyl ethyl diketone)-titanium dichloride with 20 milliliters, obtain the filbert catalyzer F of 5.3 grams.The titanium content of catalyzer F is that 1.51 heavy %, Mg content are 7.0 heavy %.
Example 7
The preparation active ingredient is the supported catalyst of cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO)) titanium chloride.
(1) preparation cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO)) titanium chloride
Method by (1) step of example 1 prepares cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO)) titanium chloride.That different is TiCl during a reacted in the step
4With the mol ratio of diphenylpropane-1,3-dione(DPPO) be 1: 2, make two (diphenylpropane-1,3-dione(DPPO)) titanium dichloride.Afterwards in c step, with the concentration of preparation the toluene solution reaction of toluene solution and cyclopentadiene sodium of two (diphenylpropane-1,3-dione(DPPO)) titanium dichloride of 47.53 heavy %, filtration, drying make cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO)) titanium chloride.
(2) preparation supported catalyst
Method by (2) step of example 1 prepares supported catalyst, that different is c) go on foot the dichloroethane solution and the two carriers reactions of magnesium chloride/kaolin that are dissolved with 0.52 gram cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO)) titanium chloride with 15 milliliters, obtain the filbert catalyzer G of 4.6 grams.The titanium content of catalyzer G is that 1.37 heavy %, Mg content are 7.9 heavy %.
Example 8
Under 70 ℃, in 3 liters of stainless steel autoclaves, feed ethene, and to keep its pressure be 0.8MPa, adds the toluene solution (production of Albemarle company) of the methylaluminoxane that contains aluminium 10 heavy %, adds 300 milliliters of the hexane solutions of catalyst A again, 70 ℃ of following polymerizations 2 hours, use the HCl termination reaction, obtain polyethylene product, catalyst activity and polymer property see Table 1.
Example 9
Method by example 8 is that Primary Catalysts carries out polymerization with the catalyst A, and different is that promotor is the hexane solution (production of Yanshan Petrochemical company) that contains the triisobutyl aluminium of aluminium 10 heavy %, and catalyst activity and polymer property see Table 1.
Example 10
Carry out the high-pressure ethylene copolymerization with catalyzer of the present invention.Method by example 8 is that Primary Catalysts carries out polymerization with the catalyst A, and adds hexene co-monomer when polymerization, and catalyst activity and polymer property see Table 1.
Example 11～17
Following example carries out the reaction of normal pressure ethylene homo.
250 milliliters of round-bottomed flasks are vacuumized the back with nitrogen purging three times, feed ethene behind the emptying nitrogen, keep-uping pressure is 0.1MPa, adds toluene solution, 50 milliliters of exsiccant hexanes and the catalyzer of the present invention of MAO, and the HCl termination reaction is used in 50 ℃ of polymerizations 1 hour.Each example catalyst system therefor, catalytic activity and polymer property see Table 1.
Table 1
| Instance number | The catalyzer numbering | Polymerization pressure (MPa) | Comonomer | The Al/Ti mol ratio | Catalytic activity * 10 -5, gram polyethylene/mole titanium hour | M w×10 -4 | M w/Mn |
| 8 | A | 0.8 | - | 200 | 86.5 | 92.6 | 4.5 |
| 9 | A | 0.8 | - | 200 | 24.5 | 99.1 | 4.7 |
| 10 | A | 0.8 | 30 milliliters of hexenes | 200 | 46.5 | 70.7 | 4.4 |
| 11 | A | 0.1 | - | 1000 | 5.36 | ||
| 12 | B | 0.1 | - | 1000 | 8.51 | 101.3 | 4.7 |
| 13 | C | 0.1 | - | 1000 | 7.91 | ||
| 14 | D | 0.1 | - | 1000 | 1.31 | 98.1 | 5.3 |
| 15 | E | 0.1 | - | 1000 | 3.63 | - | - |
| 16 | F | 0.1 | - | 1000 | 3.23 | - | - |
| 17 | G | 0.1 | - | 1000 | 3.17 | - | - |
Claims (12)
1, a kind of polyethylene catalysts of loaded by semi-metallocene comprises two carriers of magnesium halide/kaolin and the semi-metallocene active ingredient with formula (I) expression formula, and the titanium content in the described catalyzer is 0.1～10 heavy %, and Mg content is 2.5～20.0 heavy %,
R can be identical or inequality with R ' in the formula (I), 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
1, two adjacent substituting groups on its skeleton can be connected with each other and form the above condensed ring of binary, R
1Be selected from hydrogen, C
1～C
18Alkyl or perfluoroalkyl, C
6～C
24Aralkyl or alkaryl, X is a halogen, n is 1～3 integer.
2,, it is characterized in that described R and R ' are respectively C according to the described catalyzer of claim 1
1～C
3Alkyl, C
1～C
3Perfluoroalkyl or C
6～C
9Alkaryl, Cp ' is C
1～C
4The alkyl list replaces or polysubstituted cyclopentadienyl, fluorenyl or indenyl.
3, according to the described catalyzer of claim 1, it is characterized in that the Cp ' that is reached is cyclopentadienyl, fluorenyl or indenyl, X is a chlorine.
4, according to described catalysis Liu of claim 1, it is characterized in that described magnesium halide is a magnesium chloride, the titanium content in the catalyzer is 0.5～5.0 heavy %.
5, according to described any one catalyzer of claim 1～4, it is characterized in that described R and R ' they are methyl or phenyl, Cp ' is cyclopentadienyl, butyl cyclopentadienyl, bad pentadienyl of pentamethyl-, indenyl or fluorenyl.
6, the described Preparation of catalysts method of a kind of claim 1, comprise anhydrous magnesium halide is dissolved in the tetrahydrofuran-ethyl alcohol mixed solvent, again with the abundant contact reacts of kaolin, thereafter adding unreactive hydrocarbons solvent is placed to precipitation and fully separates out, filtration, drying make carrier, the toluene solution processing back of this carrier with methylaluminoxane fully contacted with the semi-metallocene active ingredient that is dissolved in polar organic solvent, add unreactive hydrocarbons solvent to precipitation and fully separates out, then filtration, drying.
7, in accordance with the method for claim 6, it is characterized in that tetrahydrofuran (THF) and alcoholic acid volume ratio are 5～25: 1 in the tetrahydrofuran-ethyl alcohol mixed solvent.
8, in accordance with the method for claim 6, it is characterized in that magnesium halide solution and kaolinic temperature of reaction are 30～70 ℃.
9, in accordance with the method for claim 6, it is characterized in that described polar organic solvent is selected from C
1～C
3Chloroparaffin, the temperature of reaction of carrier and semi-metallocene active ingredient is 10～70 ℃.
10, in accordance with the method for claim 6, it is characterized in that described unreactive hydrocarbons solvent is selected from C
5～C
20Alkane, in the carrier in magnesium and the semi-metallocene mol ratio of titanium be 5～500: 1.
11, in accordance with the method for claim 6, it is characterized in that described kaolin needs to carry out activation treatment at 200～550 ℃.
12, in accordance with the method for claim 6, when it is characterized in that in the Preparation of Catalyst handling carrier and loaded by semi-metallocene active ingredient with methylaluminoxane, earlier carrier is used with reactant and all nonreactive dispersion agent of resultant and disperseed, dispersion agent is selected from toluene or methylene dichloride, and the kaolin activation temperature is 300～500 ℃.
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| CNB011237589A CN1156496C (en) | 2001-07-31 | 2001-07-31 | Polythene catalyst loaded by double-carrier of magnesium chloride/kaolin and its preparation method |
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| CN1156496C true CN1156496C (en) | 2004-07-07 |
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