CN1345887A - Semi-metallocene supported polyvinyl catalyst and preparation method thereof - Google Patents
Semi-metallocene supported polyvinyl catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a polyethylene catalyst and its preparation method. Said catalyst includes inorganic chloride carrier and sem-metallocene active component loaded on said carrier. Said invention also provides the general formula expression of said semi-metallocene active component, and the titanium content being in the catalyst is 0.1-10 wt%. Said load catalyst is matched with organic aluminium catalyst promoter, and can be used for homopolymerization and copolymerization of ethylene and alpha-olefin, and possesses high polymerization reaction activity.
Description
The present invention relates to a kind of polyethylene catalysts and preparation method of loaded by semi-metallocene active ingredient.Specifically, be 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.
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.
People such as K.Soga are at J.Polym.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 291-311 delivers, this catalyzer and triisobutyl aluminum cocatalyst are used and can prepare polypropylene, and have high polymerization activity.
The purpose of this invention is to provide a kind of is the loading type polyethylene catalysts and preparation method thereof of active ingredient with the semi-metallocene.
Another object of the present invention provides the method that above-mentioned loading type semi-metallocene catalyst carries out vinyl polymerization of using.
We find, what will be used to prepare syndiotactic polystyrene is the catalyzer that the semi-metallocene active constituent loading of part makes behind the butter carrier with the beta-diketo derivative, can be used for the catalyzer of ethylene polymerization, and has advantages of high catalytic activity.
Specifically, catalyzer of the present invention comprises the butter carrier and is carried on the semi-metallocene active ingredient that has following general expression on this carrier, and the titanium content in the described catalyzer is 0.1～10 heavy %, preferred 0.5～5.0 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, preferred chlorine, n is 1～3 integer.
The preferred C of R and R ' in the 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 the preparation described butter carrier of loaded catalyst, 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.
The preparation method of the described semi-metallocene active ingredient of 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 adding Cp ' M, react at-15～25 ℃, remove the compound that desolvates and be drying to obtain formula (I), the M among described Cp ' M is a basic metal, preferred sodium.
Before the aforesaid method drying, the most handy ether washed solid, or as required the solid matter recrystallization is purified, the recrystallization solvent for use is a polar organic solvent, as halogenated alkane.Optional 50～60 ℃ of drying temperature, time of drying is unrestricted, preferred 3～12 hours.
When synthesizing the beta diketone titanium compound, method is with beta-diketone compound and TiX preferably
4Make diethyl ether solution respectively, the diethyl ether solution with two kinds of materials mixes then, is heated to reflux temperature reaction 1～2 hour, filters or removes and desolvate, and washs to filtrate colourless with ether.The used preferred titanium chloride of halogenated titanium during reaction.
The general formula that above-mentioned synthetic beta diketone titanium compound uses is R '-C (O)-CH
2The preferred C of R and R ' in the beta-diketone compound of-C (O)-R
1～C
3Alkyl, C
1～C
3Perfluoroalkyl or C
6～C
9Alkaryl.Preferred beta-diketone compound is methyl ethyl diketone, diphenylpropane-1,3-dione(DPPO), praseodynium.
Preferred beta diketone titanium compound is (methyl ethyl diketone) titanous chloride, two (methyl ethyl diketone) titanium dichloride, tri acetylacetonato titanium chloride, (diphenylpropane-1,3-dione(DPPO)) titanous chloride, two (diphenylpropane-1,3-dione(DPPO)) titanium dichloride, three (diphenylpropane-1,3-dione(DPPO)) titanium chloride, (trifluoroacetylacetone) titanous chloride, two (trifluoroacetylacetone) titanium dichloride, three (trifluoroacetylacetone) titanium chloride.
The preparation method of described Cp ' M is in ether solvent, will have the Compound C p ' H of cyclopentadienyl skeleton and the alkali metal compound of equimolar amount and react, and removes then and desolvates, and obtains containing an alkali metal salt of cyclopentadienyl skeleton part.During reaction, temperature is controlled to be-44～150 ℃, preferred-10～115 ℃, reaction times is 1～5 hour, can earlier alkali metal compound be dissolved in the ether during operation, adds the ethereal solution of Cp ' H again, also can be opposite, the add-on of ether solvent should be controlled at 3～5 times of reactant gross weight.
The used alkali metal compound of preparation Cp ' M is selected from basic metal, alkali-metal hydride, alkylide or amides, and the alkyl in the described alkylide is C
1～C
24Alkyl, as butyl, comparatively preferred alkali metal compound is sodium, potassium, butyllithium, sodium hydride, potassium hydride KH, sodium amide or potassium amide.Ether solvent is ether or tetrahydrofuran (THF).
Preparation of catalysts method of the present invention comprises: the butter solution that will be dissolved in tetrahydrofuran (THF) fully contacts with the semi-metallocene solution that is dissolved in polar organic solvent, in mixing solutions, add non-polar organic solvent then, be placed to precipitation and fully separate out, filter drying then.During obtain solution, the consumption of tetrahydrofuran (THF) is 10～250 times of butter weight.
Described dissolving semi-metallocene active ingredient and when preparing this active ingredient the used polar organic solvent of recrystallization be selected from C
1～C
5Halogenated alkane, preferred carbonatoms is 1～3, and the halogen atom number is 1～3 a halogenated alkane, wherein is best with the chloroparaffin, chloroparaffin is methylene dichloride, trichloromethane, ethylene dichloride, tetracol phenixin preferably, and its consumption is 5～200 times of semi-metallocene active ingredient weight.
The mol ratio of butter and semi-metallocene is 5～500: 1 in the supported catalyst preparation process, preferred 5～50: 1, during the abundant contact reacts of described two kinds of solution, temperature should be controlled to be 10～70 ℃, preferred 10～30 ℃, be 0.5～72 hour duration of contact, preferred 0.5～2.0 hour, preferably adopts the mode that stirs that two kinds of solution are fully contacted.
After two kinds of solution mix fully contact in the preparation supported catalyst agent method, prepare catalyzer with coprecipitation method.The non-polar solvent that is used for co-precipitation is C
5～C
20Alkane, preferred C
5～C
8Alkane, as hexane, octane, heptane, the consumption of non-polar solvent and the volume ratio of described polar solvent are 3～50: 1.
Co-precipitation can be carried out under the condition identical with two kinds of solution contact temperature, preferred 10～30 ℃, preferred 0.5～12 hour of time of repose behind the adding non-polar solvent, after treating that precipitation is separated out fully, with isolated solids drying, preferred drying temperature is 30～50 ℃, and the time is 3～6 hours, can obtain mobile well supported catalyst.
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 or aluminum alkyl catalyst during polymerization, and polymerization temperature is 10～100 ℃, is preferably 30～80 ℃.Preferred comonomer is C during copolymerization
3～C
15Alpha-olefin, as butylene, amylene, hexene or vinylbenzene.
Described promotor aikyiaiurnirsoxan beta can be linear or cyclic, has following repeating unit:
R in the formula " is C
1～C
8Alkyl, preferable methyl, ethyl or isobutyl-, n are 5～40.Particularly preferred promotor is methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide.
The promotor aluminum alkyls is selected from triethyl aluminum, 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.
The semi-metallocene component that the present invention will be used for styrene polymerization is carried on the butter carrier, make the catalyzer after the load can be used for the homopolymerization and the copolymerization of ethene, and have high polymerization activity, as at normal pressure, during 50 ℃ of polymerizations, polymerization activity reaches 2.05 * 10
5Gram PE/ mole Ti hour, and the molecular weight of polymkeric substance is 94.2 ten thousand, and molecular weight distribution is 5.2.
Below by example in detail the present invention, but the present invention is not limited to this.
Embodiment 1
The preparation active ingredient is the supported catalyst of cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(1) preparation active ingredient 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 first hydrogen furans ,-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.Its ultimate analysis measured value (calculated value) is:
C 58.98 heavy % (59.00 heavy %), H 4.02 heavy % (3.90 heavy %).
(2) preparation supported catalyst
Get water content and put into reaction flask less than dry magnesium chloride (production of Jinzhou aluminium manufacturer) 1.2 grams of 1.0 heavy %, add 60 milliliters of exsiccant tetrahydrofuran (THF)s, 55 ℃ are reacted 1 hour formation adduct solution down.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 catalyst A in 6 hours 20 ℃ of dryings.The titanium content that records catalyst A with plasma emission spectrum (ICP) method is 1.01 heavy %.
Embodiment 2
The preparation active ingredient is the supported catalyst of butyl cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(1) preparation active ingredient butyl cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride
Method by (1) step of embodiment 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, its ultimate analysis measured value (calculated value) is:
C 63.01 heavy % (62.36 heavy %), H 5.67 heavy % (5.23 heavy %).
(2) preparation supported catalyst
Method by (2) step of embodiment 1 prepares supported catalyst, different is to be dissolved with 0.42 gram butyl cyclopentadiene-dichloromethane solution of (diphenylpropane-1,3-dione(DPPO)) titanium dichloride and the reaction of the tetrahydrofuran solution of magnesium chloride with 15 milliliters, obtains the filbert catalyst B of 0.92 gram.The titanium content of catalyst B is 0.96 heavy %.
Embodiment 3
The preparation active ingredient is the supported catalyst of indenyl-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(1) preparation active ingredient indenyl-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride
Method by (1) step of embodiment 1 prepares butyl cyclopentadiene-(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.Its ultimate analysis measured value (calculated value) is:
C 60.94 heavy % (60.29 heavy %), H 5.02 heavy % (4.18 heavy %).
(2) preparation supported catalyst
Method by (2) step of embodiment 1 prepares supported catalyst, and different is to be dissolved with 0.45 gram indenyl-dichloromethane solution of (diphenylpropane-1,3-dione(DPPO)) titanium dichloride and the reaction of the tetrahydrofuran solution of magnesium chloride with 15 milliliters, obtains the filbert catalyzer C of 0.98 gram.The titanium content of catalyzer C is 0.89 heavy %.
Embodiment 4
The preparation active ingredient is the supported catalyst of cyclopentadiene-(methyl ethyl diketone) titanium dichloride.
(1) preparation active ingredient cyclopentadiene-(methyl ethyl diketone) titanium dichloride
With concentration is 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.
Above-mentioned (methyl ethyl diketone) titanous chloride is dissolved in the solution that toluene is made 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.Its ultimate analysis measured value (calculated value) is:
C 42.39 heavy % (42.39 heavy %), H 4.22 heavy % (4.27 heavy %).
(2) preparation supported catalyst
Method by (2) step of embodiment 1 prepares supported catalyst, and different is to be dissolved with 0.57 gram cyclopentadiene-chloroform soln of (methyl ethyl diketone)-titanium dichloride and the reaction of the tetrahydrofuran solution of magnesium chloride with 15 milliliters, obtains the filbert catalyzer D of 1.02 grams.The titanium content of catalyzer D is 0.72 heavy %.
Embodiment 5
The preparation active ingredient is the supported catalyst of butyl cyclopentadiene-(methyl ethyl diketone)-titanium dichloride.
(1) preparation active ingredient butyl cyclopentadiene-(methyl ethyl diketone)-titanium dichloride
Method by embodiment 4 prepares active ingredient, and different is with butyl cyclopentadiene sodium and the reaction of (methyl ethyl diketone) titanous chloride, makes active ingredient butyl cyclopentadiene-(methyl ethyl diketone)-titanium dichloride.Its ultimate analysis measured value (calculated value) is:
C 49.69 heavy % (49.59 heavy %), H 5.86 heavy % (5.94 heavy %).
(2) preparation supported catalyst
Method by (2) step of embodiment 1 prepares supported catalyst, different is to be dissolved with 0.49 gram butyl cyclopentadiene-dichloromethane solution of (methyl ethyl diketone)-titanium dichloride and the reaction of the tetrahydrofuran solution of magnesium chloride with 15 milliliters, obtains the filbert catalyzer E of 0.91 gram.The titanium content of catalyzer E is 0.79 heavy %.
Embodiment 6
The preparation active ingredient is the supported catalyst of indenyl-(methyl ethyl diketone)-titanium dichloride.
(1) preparation active ingredient indenyl-(methyl ethyl diketone)-titanium dichloride
Method by embodiment 4 prepares active ingredient, and 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, and its ultimate analysis measured value (calculated value) is:
C 59.89 heavy % (56.14 heavy %), H 4.92 heavy % (4.17 heavy %).
(2) preparation supported catalyst
Method by (2) step of embodiment 1 prepares supported catalyst, and different is to be dissolved with 0.43 gram indenyl-dichloromethane solution of (methyl ethyl diketone)-titanium dichloride and the reaction of the tetrahydrofuran solution of magnesium chloride with 15 milliliters, obtains the filbert catalyzer F of 0.87 gram.The titanium content of catalyzer F is 0.73 heavy %.
Embodiment 7
The preparation active ingredient is the supported catalyst of cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO)) titanium chloride.
(1) preparation active ingredient cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO)) titanium chloride
Method by (1) step of embodiment 1 prepares cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO)) titanium chloride, and different is during a goes on foot, TiCl
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 goes on foot, the toluene solution of toluene solution and cyclopentadiene sodium that with the concentration of preparation is two (diphenylpropane-1,3-dione(DPPO)) titanium dichloride of 47.53 heavy % reacts, filtration, drying make cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO)) titanium chloride, and its ultimate analysis measured value (calculated value) is:
C 69.98 heavy % (70.67 heavy %), H 4.60 heavy % (4.57 heavy %).
(2) preparation supported catalyst
Method by (2) step of embodiment 1 prepares supported catalyst, different is the tetrahydrofuran solution reaction that is dissolved with the dichloroethane solution and the magnesium chloride of 0.52 gram cyclopentadiene-two (diphenylpropane-1,3-dione(DPPO)) titanium chloride with 15 milliliters, obtains the filbert catalyzer G of 1.1 grams.The titanium content of catalyzer G is 1.37 heavy %.
Embodiment 8
Following examples are carried out the high-pressure ethylene homopolymerization with catalyzer of the present invention.
Under 70 ℃, in 1 liter of stainless steel autoclave, feed ethene, and to keep its pressure be 0.7MPa, adds 90 milliliters of methylaluminoxane (MAO) toluene solutions (production of A1bemarle company) that contain aluminium 10 heavy %, adds 300 milliliters of the hexane solutions of catalyst A again, 70 ℃ of following polymerizations 1.5 hours, use the HCl termination reaction, obtain 138 gram polyethylene products, catalyst activity sees Table 1.
Embodiment 9
Carry out the reaction of normal pressure ethylene homo with catalyzer of the present invention.
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 15 milliliters of the toluene solutions of MAO, 50 milliliters of exsiccant hexanes and 5 * 10
-6Mol catalyst A.50 ℃ of polymerizations 1 hour, catalyst activity and polymer property see Table 1.
Embodiment 10～12
Following example carries out the reaction of normal pressure ethylene copolymerization with catalyzer of the present invention.
Method by embodiment 9 is that Primary Catalysts carries out polymerization with the catalyst A, adds different comonomers when polymerization, the comonomer of each embodiment and dosage, and catalyst activity sees Table 1.
Embodiment 13～14
Carry out the high-pressure ethylene homopolymerization by embodiment 8 methods, each embodiment catalyst system therefor and catalytic activity see Table 1.
Embodiment 15～20
Following examples are carried out the reaction of normal pressure ethylene homo.
Method by embodiment 9 is carried out polymerization, and each embodiment catalyst system therefor, catalytic activity and polymer property see Table 1.
Table 1
| Embodiment | The catalyzer numbering | Polymerization methods | Comonomer | The Al/Ti mol ratio | Catalytic activity * 10 -5, gram polyethylene/mole titanium hour | M w×10 -4 | ?M w/Mn |
| ????8 | ????A | High pressure | ????- | ????1200 | ????70.1 | ||
| ????9 | ????A | Normal pressure | ????- | ????1300 | ????2.05 | ????94.2 | ????5.2 |
| ????10 | ????A | Normal pressure | 10 milliliters of vinylbenzene | ????1300 | ????1.08 | ||
| ????11 | ????A | Normal pressure | 5 milliliters of hexenes | ????1300 | ????2.11 | ||
| ????12 | ????A | Normal pressure | 10 milliliters of hexenes | ????1300 | ????2.22 | ||
| ????13 | ????B | High pressure | ????- | ????1200 | ????283.2 | ||
| ????14 | ????C | High pressure | ????- | ????1200 | ????255.4 | ||
| ????15 | ????B | Normal pressure | ????- | ????1300 | ????6.07 | ????101.3 | ????4.7 |
| ????16 | ????C | Normal pressure | ????- | ????1300 | ????5.67 | ||
| ????17 | ????D | Normal pressure | ????- | ????1300 | ????0.93 | ????98.1 | ????5.3 |
| ????18 | ????E | Normal pressure | ????- | ????1300 | ????2.74 | ||
| ????19 | ????F | Normal pressure | ????- | ????1300 | ????2.61 | ||
| ????20 | ????G | Normal pressure | ???- | ????1300 | ????0.84 |
Annotate: the high pressure polymerisation condition is 70 ℃ of temperature, pressure 0.7MPa
The polymerization under atmospheric pressure condition is 50 ℃ of temperature, pressure 0.1MPa
Claims (14)
1, a kind of polyethylene catalysts comprises the butter carrier and is carried on the semi-metallocene active ingredient that has following general expression on this carrier, and the titanium content in the described catalyzer is 0.1～10 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 cyclopentadienyl, fluorenyl or indenyl.
3,, it is characterized in that described Cp ' is C according to the described catalyzer of claim 1
1～C
4The alkyl list replaces or polysubstituted cyclopentadienyl, fluorenyl or indenyl, and X is a chlorine.
4, according to the described catalyzer of claim 1, it is characterized in that described butter 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, pentamethyl-cyclopentadienyl, indenyl or fluorenyl.
6, the described Preparation of catalysts method of a kind of claim 1, comprise that the butter solution that will be dissolved in tetrahydrofuran (THF) fully contacts with the semi-metallocene solution that is dissolved in polar organic solvent, in mixing solutions, add non-polar organic solvent then, being placed to precipitation fully separates out, filter drying then.
7, in accordance with the method for claim 6, it is characterized in that described polar organic solvent is selected from C
1～C
5Halogenated alkane.
8, in accordance with the method for claim 7, it is characterized in that described polar organic solvent is the chloroparaffin that contains 1～3 carbon atom.
9, in accordance with the method for claim 6, it is characterized in that described non-polar organic solvent is selected from C
5～C
20Alkane.
10, in accordance with the method for claim 6, the mol ratio that it is characterized in that described butter and semi-metallocene is 5～500: 1
11, in accordance with the method for claim 6, it is characterized in that the temperature that described two kinds of solution fully contact is 10～70 ℃, carrying out the sedimentary time with non-polar organic solvent is 0.5～72 hour.
12, a kind of ethene polymerization method comprises that with the described catalyzer of claim 1 be Primary Catalysts, is promotor with aikyiaiurnirsoxan beta or aluminum alkyls, makes ethene or alpha-olefin carry out polymerization under polymeric reaction condition.
13, in accordance with the method for claim 12, it is characterized in that described promotor is methylaluminoxane, ethyl aikyiaiurnirsoxan beta, triethyl aluminum or triisobutyl aluminium, the Al/Ti mol ratio is 25～2000: 1 during polyreaction.
14, in accordance with the method for claim 13, it is characterized in that described alpha-olefin is ethene, butylene, amylene or hexene.
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| CN 00124667 CN1128825C (en) | 2000-09-28 | 2000-09-28 | Semi-metallocene supported polyvinyl catalyst and preparation method thereof |
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| CN 00124667 CN1128825C (en) | 2000-09-28 | 2000-09-28 | Semi-metallocene supported polyvinyl catalyst and preparation method thereof |
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| CN1128825C CN1128825C (en) | 2003-11-26 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343290C (en) * | 2002-10-18 | 2007-10-17 | 中国石油化工股份有限公司 | Metallocene catalyst for production of polyolefine with broad peak or double peaks molecular weight distribution in monoreactor and its preparation |
| CN101250238B (en) * | 2008-03-28 | 2010-06-02 | 中国石油天然气股份有限公司 | Boroxol titanocene metal catalyzer and preparation method and application thereof |
| CN104693327A (en) * | 2015-02-15 | 2015-06-10 | 北京化工大学 | Bi-metal semi-metallocene catalyst and preparation method and application thereof |
| CN105646737A (en) * | 2016-01-08 | 2016-06-08 | 中山大学 | Supported bridged bis-phenoxy IVB metal catalyst and preparation method thereof |
-
2000
- 2000-09-28 CN CN 00124667 patent/CN1128825C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343290C (en) * | 2002-10-18 | 2007-10-17 | 中国石油化工股份有限公司 | Metallocene catalyst for production of polyolefine with broad peak or double peaks molecular weight distribution in monoreactor and its preparation |
| CN101250238B (en) * | 2008-03-28 | 2010-06-02 | 中国石油天然气股份有限公司 | Boroxol titanocene metal catalyzer and preparation method and application thereof |
| CN104693327A (en) * | 2015-02-15 | 2015-06-10 | 北京化工大学 | Bi-metal semi-metallocene catalyst and preparation method and application thereof |
| CN105646737A (en) * | 2016-01-08 | 2016-06-08 | 中山大学 | Supported bridged bis-phenoxy IVB metal catalyst and preparation method thereof |
| CN105646737B (en) * | 2016-01-08 | 2018-11-02 | 中山大学 | Double phenoxy group IVB metallic catalysts of a kind of support type bridging and preparation method thereof |
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| Publication number | Publication date |
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| CN1128825C (en) | 2003-11-26 |
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