CN1371924A - High molecular nickel zirconium double activity center olefines polymerizing catalyst - Google Patents
High molecular nickel zirconium double activity center olefines polymerizing catalyst Download PDFInfo
- Publication number
- CN1371924A CN1371924A CN 02104276 CN02104276A CN1371924A CN 1371924 A CN1371924 A CN 1371924A CN 02104276 CN02104276 CN 02104276 CN 02104276 A CN02104276 A CN 02104276A CN 1371924 A CN1371924 A CN 1371924A
- Authority
- CN
- China
- Prior art keywords
- methyl
- high molecular
- alpha
- com
- diimine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The catalyst is formed from of A and B, in which the expression formula of the A is [P-(ComNi-co-S-co-ComZr)] or [SiO2-P(ComNi-co-S-co-Comzr)], P represents copolymer, S is styrene, co represents copolymerization, Com Ni represents "after-cyclopentadiene' alpha-diimine nickel base catalyst containing olefine group and ComZr represents cyclopentadiene zirconium catalyst containig olefine group. [P(ComNi-co-S-co-ComZr)] is a copolymer of alpha-diimine nickel catalyst, metallocene catalyst and styrene, and SiO2 represents silicon dioxide carrier. The B is one of methyl aluminium oxoalkane (MAO), modified methyl aluminium oxoalkane (MMAO) or [B(C6F5)3]. Said catalyst possesses high catalytic activity for catalyzing polymerization of ethene, and is suitable for gas phase and slurry polymerization.
Description
Technical field: the present invention relates to a kind of olefin polymerization catalysis, be specifically related to a kind of high molecular olefin polymerization catalysis that contains the nickel zirconium double activity center;
The invention still further relates to a kind of above-mentioned Preparation of catalysts method;
The invention still further relates to above-mentioned catalyzer in olefinic polymerization, especially the application in vinyl polymerization.
Background technology: " luxuriant back " late transition metal catalyst that originates at the end of last century is described as the third generation high activity olefin polymerization catalyst after Ziegler-Natta catalyst and metallocene catalyst, has now become the research focus of new olefine polymerization catalyst in the world wide.But traditional early transition metal catalyzer is just being brought into play enormous function in modern industry production, how becomes the important research direction of present olefinic polymerization in conjunction with the advantage of early transition metal catalyzer and late transition metal catalyst with the polyolefine material of preparation structure and performance novelty.Chinese patent (98125651.1,1998; 01140470.1,2001) and the preparation method of the preparation method of high molecular metallocene calalyst for polymerization of olefine and high molecular rear transition metal " luxuriant back " nickel base olefine polymerization catlayst disclosed respectively.The nickel zirconium double activity centers catalyse agent of relevant high molecular does not appear in the newspapers as yet, and this work adapts to industrial production device to obtaining the polymkeric substance of the desired molecular weight and the degree of branching, and there is certain meaning the aspects such as Physical Processing performance that improve polymkeric substance.
Summary of the invention: the nickel zirconium double activity site olefin polymerization catalysts that the purpose of this invention is to provide a kind of high molecular;
Another object of the present invention provides a kind of preparation method of nickel zirconium double activity site olefin polymerization catalysts of high molecular, this method adopt the IVB family metallocene compound that contains the alkene substituted radical and alpha-diimine nickel based compound under the initiator effect with styrene copolymerized, the front and back transition-metal catalyst is connected to the nickel zirconium double activity site olefin polymerization catalysts that forms high molecular on the macromolecular chain by the σ key;
The nickel zirconium double activity centers catalyse agent that the 3rd purpose of the present invention provides a kind of high molecular is in olefinic polymerization, the especially application in vinyl polymerization.
The nickel zirconium double activity centers catalyse agent of high molecular has very high catalytic activity equally to olefinic polymerization, and with composition, the distribution of control catalyst on macromolecular chain at an easy rate of front and back transition-metal catalyst high molecular, the katalysis in active centre be can bring into play to greatest extent by regulating the distribution of catalyzer on macromolecular chain, physical mechanical and the processing characteristics of improving polymkeric substance reached.In addition, the resulting polymkeric substance of high molecular nickel zirconium double activity centers catalyse agent catalysis in olefine polymerization does not contain inorganic ash content.
The catalyzer of the present invention's preparation is made up of A and B two components, and A component expression formula is [P (Com Ni-co-S-co-Com Zr)] or [SiO
2-P (Com Ni-co-S-co-Com Zr)], P represents multipolymer, and S is a polystyrene, and co represents copolymerization, and it is catalyst based that ComNi represents to contain " luxuriant back " alpha-diimine nickel of olefin group, and ComZr represents to contain the luxuriant zirconium metal species catalyzer of alkene group.[P (Com Ni-co-S-co-Com Zr)] is that it has following structure by alpha-diimine nickel catalyzator and metallocene catalyst and cinnamic multipolymer:
Wherein m is the integer of 0-4; N is the integer between the 0-100; X is Cl or Br; R
1With R
2Can be identical or different, be respectively hydrogen, methyl, sec.-propyl or the tertiary butyl; R
3Be any one of hydrogen, methyl, propyl group or butyl; R
3Be hydrogen or methyl; Q is residue of divalent or its mixture that is selected from following ring compound:
Wherein, R
5With R
6Can be identical or different, be respectively methyl, ethyl, propyl group or heterocycle: SiO
2The expression silica supports is immobilized with high molecular catalyzer [P (Com Ni-co-S-co-Com Zr)].The B component is methylaluminoxane (MAO), improvement methylaluminoxane (MMAO) or penta phenyl fluoride boron [B (C
6F
5)
3] wherein any one.The Preparation of catalysts process is as follows:
The N-alkylene aniline that substituted aromatic amines and alkylene chloro or alkylene bromine generate is reset in the presence of Zinc Chloride Anhydrous, obtains 4-alkylene arylamine, productive rate 25-71%.
R wherein
1With R
2Can be identical or different, be respectively H, methyl, sec.-propyl or the tertiary butyl, R
3Be H, methyl, ethyl, propyl group or butyl.
Under the catalysis of formic acid, acetate, trifluoroacetic acid and hydrochloric acid, in acid and alcoholic solvent system, carry out condensation reaction with the α-diketone shown in the following formula
Obtain the alpha-diimine part that contains olefin group shown in the following formula, productive rate 72-84%;
Under the anhydrous and oxygen-free condition, carry out above-mentioned part and NiX
2, wherein X is Cl or Br, coordination reaction, obtain alpha-diimine Ni (II) title complex that following formula contains olefin group, productive rate 92-98%;
With the Tetrabutyl amonium bromide is consisting of phase-transferring agent, and cyclopentadiene and haloolefin effect obtain following alkylene cyclopentadiene, productive rate 40-70%:
Wherein m is the integer of 0-4, R
4Be hydrogen or methyl.
In the tetrahydrofuran (THF) system, handle above-mentioned alkylene cyclopentadiene with the n-BuLi that waits mole number, with the ZrCl of equivalent
4Reaction obtains following alkylene metallocene catalyst, productive rate 60-75%.
Wherein X is Cl or Br; M is the integer of 0-4; R
4Be hydrogen or methyl.
Under the anhydrous and oxygen-free condition, to contain alpha-diimine Ni (II) title complex of olefin group and contain the metallocene catalyst of alkene at AIBN, AIBN is that azo isobutyl second is fine, cause down with styrene copolymerized, make catalyzer pass through σ key and Polyethylene Chain and link, obtain as shown in the formula high molecular dual-active olefin polymerization catalysis:
Wherein m is the integer of 0-4; N is the integer between the 0-100; X is Cl or Br; R
1With R
2Can be identical or different, be respectively hydrogen, methyl, sec.-propyl or the tertiary butyl; R
3Be any one of hydrogen, methyl, propyl group or butyl; R
3Be hydrogen or methyl; Q is residue of divalent or its mixture that is selected from following ring compound:
Wherein, R
5With R
6Can be identical or different, be respectively methyl, ethyl, propyl group or heterocycle: SiO
2The expression silica supports is immobilized with high molecular catalyzer [P (Com Ni-co-S-co-Com Zr)].
The A component is at the cocatalyst B component, and the B component is methylaluminoxane (MAO), improvement methylaluminoxane (MMAO) or penta phenyl fluoride boron [B (C
6F
5)
3] effect under, catalysis in olefine polymerization under 1-20 normal atmosphere, the active amt level is 10
5-10
7GPE (molNih)
-1
Embodiment is as follows: embodiment 1: the preparation of allylic arylamine
With 2,0.2 mole of 6-diisopropyl aniline and 0.1 mole of reflux of allyl chloric ether 8 hours, cooling is placed and is spent the night, in impouring 400 ml waters, with sodium hydroxide solution alkalization, extracted with diethyl ether, vacuum decompression distill N-allyl alkyl-2,6-diisopropyl aniline 18.33 gram. productive rate is 84%.With 100 milliliters of toluene is that solvent adds N-allyl alkyl-2,0.1 mole of 0.084 mole of 6-diisopropyl aniline and Zinc Chloride Anhydrous, refluxed 5 hours under the argon gas atmosphere, alkalize in the cooling back impouring aqueous sodium hydroxide solution, isolate organic layer, lower floor's insolubles is dissolved in the concentrated hydrochloric acid of heat, again in the above-mentioned ether extraction liquid of impouring, anhydrous magnesium sulfate drying, underpressure distillation gets 4-allyl alkyl-2 behind the vacuum concentration, 6-diisopropyl aniline 12.92 grams, productive rate is 71%.Embodiment 2: the preparation of allylic arylamine
With 0.1 mole of 2-tertiary butyl aniline and 0.05 mole of reflux of 1-bromo-2-butylene alkyl 10 hours, cooling was placed and is spent the night, in impouring 200 ml waters, alkalize with sodium hydroxide solution, extracted with diethyl ether, vacuum decompression are distilled to such an extent that N-(2-methylpropenyl)-2-tertiary butyl aniline 5.35 restrains productive rate 53%.With 200 milliliters of toluene is that solvent adds 0.2 mole of N-(2-methylpropenyl)-0.2 mole of 2-tertiary butyl aniline and Zinc Chloride Anhydrous, refluxed 8 hours under the argon gas atmosphere, alkalize in the cooling back impouring aqueous sodium hydroxide solution, isolate organic layer, lower floor's insolubles is dissolved in the concentrated hydrochloric acid of heat, again in the above-mentioned ether extraction liquid of impouring, and anhydrous magnesium sulfate drying, underpressure distillation gets 4-(2-methylpropenyl)-2-tertiary butyl aniline 24.89 grams, productive rate 61% behind the vacuum concentration.Embodiment 3: the preparation of allylic arylamine
With 2,0.12 mole of 6-xylidine and 0.06 mole of reflux of 1-bromo-2-amylene 9 hours, cooling is placed and is spent the night, in impouring 300 ml waters, alkalize with sodium hydroxide solution, extracted with diethyl ether, vacuum decompression distill N-(2-ethyl propylene base)-2,6-xylidine 3.72 gram. productive rate is 33%.With 80 milliliters of toluene is that solvent adds N-(2-ethyl propylene base)-2,0.05 mole of 0.05 mole of 6-xylidine and Zinc Chloride Anhydrous, refluxed 7 hours under the argon gas atmosphere, alkalize in the cooling back impouring aqueous sodium hydroxide solution, isolate organic layer, lower floor's insolubles is dissolved in the concentrated hydrochloric acid of heat, again in the above-mentioned ether extraction liquid of impouring, anhydrous magnesium sulfate drying, reduce pressure behind the vacuum concentration 4-allyl alkyl-2,6-xylidine 2.77 grams, productive rate is 29%.Embodiment 4: the preparation of allylic arylamine
With 2,0.1 mole of 6-diisopropyl aniline and 0.05 mole of reflux of 1-bromo-2-heptene 10 hours, cooling is placed and is spent the night, in impouring 300 ml waters, alkalize with sodium hydroxide solution, extracted with diethyl ether, vacuum decompression distill N-(2-butyl propenyl)-2,6-diisopropyl aniline 4.09 gram. productive rate is 30%.With 50 milliliters of toluene is that solvent adds N-(2-butyl propenyl)-2,0.05 mole of 0.05 mole of 6-diisopropyl aniline and Zinc Chloride Anhydrous, refluxed 8 hours under the argon gas atmosphere, alkalize in the cooling back impouring aqueous sodium hydroxide solution, isolate organic layer, lower floor's insolubles is dissolved in the concentrated hydrochloric acid of heat, again in the above-mentioned ether extraction liquid of impouring, anhydrous magnesium sulfate drying, underpressure distillation gets 4-(2-butyl allyl group)-2 behind the vacuum concentration, 6-diisopropyl aniline 3.44 grams, productive rate is 25%.Embodiment 5: contain the preparation of the diimine bitooth ligand of two olefin groups
2 mmoles α-acenaphthene ketone and 4 mmole 4-allyl groups-2, the 6-diisopropyl aniline is dissolved in 20 milliliters of acetate, after the reflux 1 hour, cool to room temperature, obtain solid precipitation, filter, according to this with acetate washing (3 * 20 milliliters), normal hexane washing (3 * 20 milliliters), vacuum-drying promptly gets alpha-diimine ligand compound C
42H
48N
21.0g, productive rate 84%.Embodiment 6: contain the preparation of the diimine bitooth ligand of two olefin groups
3 mmole α-dimethyl diketone and 6 mmole 4-(2-methacrylic)-2-tertiary butyl aniline are dissolved in 30 ml methanol, adding 3-5 drips formic acid and makes catalyzer, after the reflux 1 hour, cool to room temperature, obtain solid precipitation, filter, use methanol wash (3 * 20 milliliters), normal hexane washing (3 * 20 milliliters) according to this, vacuum-drying promptly gets alpha-diimine ligand compound C
36H
52N
21.2g, productive rate 80%.Embodiment 7: contain the preparation of the diimine bitooth ligand of two olefin groups
2.5 mmole α-cyclohexanedione and 5 mmole 4-allyl groups-2, the 6-xylidine is dissolved in 25 milliliters of ethanol, add 3-5 and drip the hydrochloric acid acid as catalyst, after the reflux 1 hour, cool to room temperature obtains solid precipitation, filter, use washing with alcohol (3 * 20 milliliters), normal hexane washing (3 * 20 milliliters) according to this, vacuum-drying promptly gets alpha-diimine ligand compound C
28H
34N
21.0g, productive rate 72%.Embodiment 8: contain the preparation of the diimine bitooth ligand of two olefin groups
2.5 mmole α-phenanthrene dione and 5 mmole 4-(2-butyl allyl group)-2, the 6-diisopropyl aniline is dissolved in 30 ml methanol, after the reflux 1 hour, cool to room temperature, obtain solid precipitation, filter, use methanol wash (3 * 20 milliliters), normal hexane washing (3 * 20 milliliters) according to this, vacuum-drying promptly gets alpha-diimine ligand compound C
52H
66N
21.5g, productive rate 82%.Embodiment 9: the alpha-diimine nickel base Preparation of catalysts that contains two olefin groups
Preparation of catalysts is carried out under the anhydrous and high-purity argon gas protective condition in anaerobic.With the 30ml methylene dichloride is solvent, with diimide ligand 1mmol and 1mmol[Ni (DME) Br that obtains among the embodiment 5
2] (DME: dimethyl second diether) at room temperature stirred 12 hours, vacuum concentration removes and desolvates, and with 50ml ether washing precipitation 3-5 time, vacuum-drying gets the catalyst based C of alpha-diimine nickel
42H
48N
2NiBr
20.8g, productive rate 98%.Embodiment 10: the alpha-diimine nickel base Preparation of catalysts that contains two olefin groups
Preparation of catalysts is carried out under the anhydrous and high-purity argon gas protective condition in anaerobic.With the 40ml methylene dichloride is solvent, with diimide ligand 1mmol and 1mmol[Ni (DME) Cl that obtains among the embodiment 6
2] (DME: dimethyl second diether) at room temperature stirred 48 hours, vacuum concentration removes and desolvates, and with 50ml ether washing precipitation 3-5 time, vacuum-drying gets the catalyst based C of alpha-diimine nickel
36H
52N
2NiCl
20.6g, productive rate 98%.Embodiment 11: the alpha-diimine nickel base Preparation of catalysts that contains two olefin groups
Preparation of catalysts is carried out under the anhydrous and high-purity argon gas protective condition in anaerobic.With the 30ml methylene dichloride is solvent, with diimide ligand 0.5mmol and 0.5mmol[Ni (DME) Br that obtains among the embodiment 7
2] (DME: dimethyl second diether) at room temperature stirred 24 hours, vacuum concentration removes and desolvates, and with 50ml ether washing precipitation 3-5 time, vacuum-drying gets the catalyst based C of alpha-diimine nickel
28H
34N
2NiBr
20.3g, productive rate 96%.Embodiment 12: the alpha-diimine nickel base Preparation of catalysts that contains two olefin groups
Preparation of catalysts is carried out under the anhydrous and high-purity argon gas protective condition in anaerobic.With the 40ml methylene dichloride is solvent, with diimide ligand 1mmol and 1mmol[Ni (DME) Cl that obtains among the embodiment 8
2] (DME: dimethyl second diether) at room temperature stirred 72 hours, vacuum concentration removes and desolvates, and with 50ml ether washing precipitation 3-5 time, vacuum-drying gets the catalyst based C of alpha-diimine nickel
42H
64N
2NiCl
20.7g, productive rate 92%.The preparation of embodiment 13 alkylene cyclopentadiene
33% the NaOH that in glass Schlenk bottle, adds 100mL successively, 0.5mol cyclopentadiene, 0.5mol chlorallylene, at the 2g Tetrabutyl amonium bromide is under the consisting of phase-transferring agent, stirred 2 hours in the ice-water bath, after stirring 6 hours under the room temperature, oil phase is washed till neutrality, after adopting the Anhydrous potassium carbonate drying, obtain allyl group cyclopentadiene 36.75 under the underpressure distillation.Productive rate 70.0%.The preparation of embodiment 14 alkylene cyclopentadiene
33% the NaOH that in glass Schlenk bottle, adds 120mL successively, 0.6mol cyclopentadiene, 0.5mol 3-bromine 1-butylene, at the 3g Tetrabutyl amonium bromide is under the consisting of phase-transferring agent, stirred 2 hours in the ice-water bath, after stirring 7 hours under the room temperature, oil phase is washed till neutrality, after adopting the Anhydrous potassium carbonate drying, obtain 3-cyclopentadienyl-1-butylene 26.78g under the underpressure distillation.Productive rate 45.01%.The preparation of embodiment 15 alkylene metallocene catalysts
4.14mmol joins in the tetrahydrofuran solution with the allyl group cyclopentadiene, and under the condition that cryosel is bathed, the n-BuLi of mole numbers such as dropping at room temperature stirred 2 hours, adds the ZrCl that contains equivalent then lentamente
4Tetrahydrofuran solution, solution is scarlet, stirring reaction is 6 hours under the room temperature, boils off solvent, adds the centrifugal lithium salts of removing of toluene, and clear liquid is drained, and promptly gets product C for several times with hexane wash again
16H
16ZrCl
20.574g, productive rate 75%.The preparation of embodiment 16 alkylene metallocene catalysts
With 3-cyclopentadienyl-1-butylene 2.17mmol, allyl group cyclopentadiene 2.17mmol joins in the tetrahydrofuran solution, under the condition that cryosel is bathed, drips the n-BuLi of 4.34mmol, at room temperature stirs 3 hours, adds the TiCl that contains equivalent then lentamente
4Tetrahydrofuran solution, solution is scarlet, stirring reaction is 8 hours under the room temperature, boils off solvent, adds the centrifugal lithium salts of removing of toluene, and clear liquid is drained, and promptly gets product C for several times with hexane wash again
17H
18TiCl
20.444g, productive rate 60%.Embodiment 17: the preparation of the olefin polymerization catalysis A of high molecular double activity center component
Under the anaerobic anhydrous condition, with " luxuriant back " the catalyst based C of alpha-diimine nickel that contains olefin group that obtains among the embodiment 9
42H
48N
2NiBr
22mmol, the luxuriant Zirconium catalyzer C that contains olefin group that obtains among the embodiment 15
16H
16ZrCl
22mmol, vinylbenzene 5ml, Diisopropyl azodicarboxylate 0.05g joins successively in the toluene that steamed and mixes, then copolymer-1 2 hours in 80 ℃ oil bath.Concentrate under heating condition, make precipitation agent with normal hexane, get the solid powder, with normal hexane washing 3-5 time, vacuum-drying gets catalyst A component P[(C again
42H
48N
2NiBr
2)-co-S-co-(C
16H
16ZrCl
2)], measuring nickel content is 0.216wt%, the content of Zirconium is 0.444wt%.Embodiment 18: the preparation of the olefin polymerization catalysis A of high molecular double activity center component
Under the anaerobic anhydrous condition, with " luxuriant back " the catalyst based C of alpha-diimine nickel that contains olefin group that obtains among the embodiment 10
36H
52N
2NiBr
210mmol, the luxuriant Zirconium catalyzer C that contains olefin group that obtains among the embodiment 16
17H
18ZrCl
210mmol, vinylbenzene 10ml, Diisopropyl azodicarboxylate 0.14g joins successively in the toluene that steamed and mixes, then copolymer-1 2 hours in 80 ℃ oil bath.Concentrate under heating condition, make precipitation agent with normal hexane, get the solid powder, with normal hexane washing 3-5 time, vacuum-drying gets catalyst A component P[(C again
36H
52N
2NiBr
2)-co-S-co-(C
17H
18ZrCl
2)], measuring nickel content is 0.201wt%, the content of Zirconium is 0.532wt%.Embodiment 19: the preparation of silicon dioxide carried high molecular dual-active olefin polymerization catalysis
Under the anaerobic anhydrous condition, take by weighing silica supports 5 grams, vacuum-drying added vinylbenzene 5ml and Vinylstyrene 0.5ml after 12 hours, 70 pre-polymerizations 20 minutes, again with " luxuriant back " the catalyst based C of alpha-diimine nickel that contains olefin group that obtains among the embodiment 9
42H
48N
2NiBr
22mmol, the luxuriant Zirconium catalyzer C that contains olefin group that obtains among the embodiment 15
16H
16ZrCl
22mmol, Diisopropyl azodicarboxylate 0.05g joins successively in the toluene that steamed and mixes, then copolymer-1 2 hours in 80 ℃ oil bath.Concentrate to take out under heating condition and desolvate, precipitation is washed 3-5 time with normal hexane, and vacuum-drying gets catalyst A component S iO
2-P[(C
42H
48N
2NiBr
2)-co-S-co-(C
16H
16ZrCl
2)], measuring nickel content is 0.153wt%, the content of Zirconium is 0.387wt%.Embodiment 20: the preparation of silicon dioxide carried high molecular dual-active olefin polymerization catalysis
Under the anaerobic anhydrous condition, take by weighing silica supports 10 grams, vacuum-drying added vinylbenzene 10ml and Vinylstyrene 1ml after 12 hours, 70 pre-polymerizations 20 minutes, again with " luxuriant back " the catalyst based C of alpha-diimine nickel that contains olefin group that obtains among the embodiment 10
36H
52N
2NiBr
210mmol, the luxuriant Zirconium catalyzer C that contains olefin group that obtains among the embodiment 16
17H
18ZrCl
210mmol, Diisopropyl azodicarboxylate 0.14g joins successively in the toluene that steamed and mixes, then copolymer-1 2 hours in 80 ℃ oil bath.Concentrate to take out under heating condition and desolvate, precipitation is washed 3-5 time with normal hexane, and vacuum-drying gets catalyst A component S iO
2-P[(C
36H
52N
2NiBr
2)-co-S-co-(C
17H
18ZrCl
2)], measuring nickel content is 0.198wt%, the content of Zirconium is 0.479wt%.Embodiment 21: ethene homogeneous phase and heterogeneous polymerization
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the high molecular catalyzer 1.136 μ mol (pressing Al/M=500), the ethene that add toluene 50ml, methylaluminoxane 0.45ml according to this in reaction system, are obtained by embodiment 17 reacted 0.5 hour in 20 ℃, with the ethanolic soln termination reaction that contains 1% hydrochloric acid, products therefrom is filtered, with washing with alcohol 3 times, and, getting polyethylene 0.137g in 40 ℃ of vacuum-dryings 24 hours, activity is 2.41 * 10
5GPE/ (mol Ni h).Embodiment 22: ethene homogeneous phase and heterogeneous polymerization
Operation is with embodiment 19, and methylaluminoxane 2.0ml (pressing Al/Ni=4000) gets polyethylene 0.14g, and activity is 2.54 * 10
5G PE/ (mol Ni h).Embodiment 23: ethene homogeneous phase and heterogeneous polymerization
Operation is with embodiment 19, methylaluminoxane 0.9ml (pressing Al/Ni=1743), and 70 ℃ of following polymerizations get polyethylene 0.42g, and activity is 3.47 * 10
6G PE/ (mol Ni h).Embodiment 24: ethene homogeneous phase and heterogeneous polymerization
Vinyl polymerization carries out under the anhydrous and oxygen-free condition, the high molecular catalyzer 1.136 μ mol (pressing Al/M=500), the ethene that add toluene 50ml, methylaluminoxane 0.45ml according to this in reaction system, are obtained by embodiment 19 reacted 0.5 hour in 20 ℃, with the ethanolic soln termination reaction that contains 1% hydrochloric acid, products therefrom is filtered, with washing with alcohol 3 times, and, getting polyethylene 0.10g in 40 ℃ of vacuum-dryings 24 hours, activity is 1.72 * 10
5GPE/ (mol Ni h).Embodiment 25: ethene homogeneous phase and heterogeneous polymerization
Operation is with embodiment 22, and methylaluminoxane 2.0ml (pressing Al/Ni=4000) gets polyethylene 0.183g, and activity is 3.22 * 10
5G PE/ (mol Ni h).Embodiment 26: ethene homogeneous phase and heterogeneous polymerization
Operation in 50 ℃ of polymerizations, gets polyethylene 0.255g with embodiment 22, and activity is 2.24 * 10
5G PE/ (mol Ni h).Embodiment 27: ethene homogeneous phase and heterogeneous polymerization
Operation is with embodiment 22, and in 50 ℃, polymerization under 7 normal atmosphere gets polyethylene 1.7g, and activity is 3.0 * 10
6G PE/ (mol Ni h).
Embodiment 28: ethene homogeneous phase and heterogeneous polymerization
Operation is with embodiment 25, and ethylene pressure is 20 normal atmosphere, in 12 ℃ of polymerizations, gets polyethylene 7.31g, and activity is 1.11 * 10
7G PE/ (mol Ni h).
Claims (6)
1. the nickel zirconium double activity site olefin polymerization catalysts of a high molecular is made up of A and B two components, it is characterized in that A component expression formula is [P (Com Ni-co-S-co-Com Zr)] or [SiO
2-P (Com Ni-co-S-co-Com Zr)], P represents multipolymer, S is a polystyrene, co represents copolymerization, it is catalyst based that ComNi represents to contain olefin group " luxuriant back " alpha-diimine nickel, ComZr represents to contain the luxuriant zirconium metal species catalyzer of alkene group, and [P (Com Ni-co-S-co-Com Zr)] is that it has following structure by alpha-diimine nickel catalyzator and metallocene catalyst and cinnamic multipolymer:
Wherein m is the integer of 0-4; N is the integer between the 0-100; X is Cl or Br; R
1With R
2Can be identical or different, be respectively hydrogen, methyl, sec.-propyl or the tertiary butyl; R
3Be any one of hydrogen, methyl, propyl group or butyl; R
3Be hydrogen or methyl; Q is residue of divalent or its mixture that is selected from following ring compound:
Wherein, R
5With R
6Can be identical or different, be respectively methyl, ethyl, propyl group or heterocycle: SiO
2The expression silica supportsization.The B component is methylaluminoxane (MAO), improvement methylaluminoxane (MMAO) or penta phenyl fluoride boron [B (C
6F
5)
3] wherein any one.
2. method for preparing the nickel zirconium double activity site olefin polymerization catalysts A component of the described high molecular of claim 1 comprises:
The N-alkylene aniline that substituted aromatic amines and alkylene chloro or alkylene bromine generate is reset in the presence of Zinc Chloride Anhydrous, obtains 4-alkylene arylamine, productive rate 25-71%:
R wherein
1With R
2Can be identical or different, be respectively H, methyl, sec.-propyl or the tertiary butyl, R
3Be H, methyl, ethyl, propyl group or butyl;
Under the catalysis of formic acid, acetate, trifluoroacetic acid and hydrochloric acid, in acid and alcoholic solvent system, carry out condensation reaction with the α-diketone shown in the following formula
Obtain the alpha-diimine part that contains olefin group shown in the following formula, productive rate 72-84%;
Under the anhydrous and oxygen-free condition, with above-mentioned part and NiX
2, wherein X is Cl or Br, coordination reaction obtains alpha-diimine Ni (II) title complex that following formula contains olefin group, productive rate 92-98%;
With the Tetrabutyl amonium bromide is consisting of phase-transferring agent, and cyclopentadiene and haloolefin effect obtain following alkylene cyclopentadiene, productive rate 40-70%:
Wherein m is the integer of 0-4, R
4Be hydrogen or methyl;
In the tetrahydrofuran (THF) system, handle above-mentioned alkylene cyclopentadiene with the n-BuLi that waits mole number, with the ZrCl of equivalent
4Reaction obtains following alkylene metallocene catalyst, productive rate 60-75%;
Wherein X is Cl or Br; M is the integer of 0-4; R
4Be hydrogen or methyl;
Under the anhydrous and oxygen-free condition, to contain alpha-diimine Ni (II) title complex of olefin group and contain the metallocene catalyst of alkene at AIBN, AIBN is that azo isobutyl second is fine, cause down with styrene copolymerized, make catalyzer pass through σ key and Polyethylene Chain and link, obtain as shown in the formula high molecular dual-active olefin polymerization catalysis:
Wherein m is the integer of 0-4; N is the integer between the 0-100; X is Cl or Br; R
1With R
2Can be identical or different, be respectively hydrogen, methyl, sec.-propyl or the tertiary butyl; R
3Be any one of hydrogen, methyl, propyl group or butyl; R
3Be hydrogen or methyl; Q is residue of divalent or its mixture that is selected from following ring compound:
Wherein, R
5With R
6Can be identical or different, be respectively methyl, ethyl, propyl group or heterocycle: SiO
2The expression silica supports is immobilized with high molecular catalyzer [P (Com Ni-co-S-co-Com Zr)];
The A component is at the cocatalyst B component, and the B component is methylaluminoxane (MAO), improvement methylaluminoxane (MMAO) or penta phenyl fluoride boron [B (C
6F
5)
3] effect under, catalysis in olefine polymerization under 1-20 normal atmosphere, the active amt level is 10
5-10
7GPE (molNih)
-1
3. as the nickel zirconium double activity site olefin polymerization catalysts preparation method of claim 1,2 described high moleculars, it is characterized in that in the preparation process of silicon dioxide carried high molecular alpha-diimine nickel base catalyst A component, add silica supports, solvent and catalyzer earlier, treat to add initiator after temperature rises to 70 ± 0.5 ℃, in 80 ± 0.5 ℃ of insulation polymerizations 8 hours.
4. the preparation method of " luxuriant back " alpha-diimine nickel base olefine polymerization catlayst of high molecular as claimed in claim 1, it is characterized in that producing in the polyethylene process, comprise the step of the nickel zirconium double activity site olefin polymerization catalysts A component of using the high molecular shown in the claim 1.
5. the preparation method of the nickel zirconium double activity site olefin polymerization catalysts of high molecular as claimed in claim 1, it is characterized in that producing poly polymerization pressure is 1-20atm.
6. the preparation method of the nickel zirconium double activity site olefin polymerization catalysts of high molecular as claimed in claim 1 is characterized in that producing polyethylene and adopts polymerization in homogeneous phase and heterogeneous polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02104276 CN1371924A (en) | 2002-03-04 | 2002-03-04 | High molecular nickel zirconium double activity center olefines polymerizing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02104276 CN1371924A (en) | 2002-03-04 | 2002-03-04 | High molecular nickel zirconium double activity center olefines polymerizing catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1371924A true CN1371924A (en) | 2002-10-02 |
Family
ID=4740063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02104276 Pending CN1371924A (en) | 2002-03-04 | 2002-03-04 | High molecular nickel zirconium double activity center olefines polymerizing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1371924A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7176158B2 (en) | 2002-10-25 | 2007-02-13 | Exxonmobil Chemical Patents Inc. | Polymerization catalyst composition |
| CN104926962A (en) * | 2015-05-15 | 2015-09-23 | 浙江大学 | Ethylene acenaphthylene (alpha-diimine) nickel complex/alkyl aluminum chloride combined catalyst |
| CN110483329A (en) * | 2019-08-27 | 2019-11-22 | 中国科学技术大学 | Big steric hindrance ketimide Raney nickel and its ligand compound, preparation method and application |
| CN115838449A (en) * | 2021-09-18 | 2023-03-24 | 中国科学技术大学 | Metal catalyst, preparation method thereof and olefin polymerization method |
-
2002
- 2002-03-04 CN CN 02104276 patent/CN1371924A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7176158B2 (en) | 2002-10-25 | 2007-02-13 | Exxonmobil Chemical Patents Inc. | Polymerization catalyst composition |
| CN104926962A (en) * | 2015-05-15 | 2015-09-23 | 浙江大学 | Ethylene acenaphthylene (alpha-diimine) nickel complex/alkyl aluminum chloride combined catalyst |
| CN110483329A (en) * | 2019-08-27 | 2019-11-22 | 中国科学技术大学 | Big steric hindrance ketimide Raney nickel and its ligand compound, preparation method and application |
| CN115838449A (en) * | 2021-09-18 | 2023-03-24 | 中国科学技术大学 | Metal catalyst, preparation method thereof and olefin polymerization method |
| CN115838449B (en) * | 2021-09-18 | 2024-03-29 | 中国科学技术大学 | Metal catalyst, preparation method thereof and olefin polymerization method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1784431B1 (en) | Supported metallocene catalyst, method of preparing the catalyst and method of preparing polyolefin using the catalyst | |
| EP2492291B1 (en) | Method for preparing a metallocene-supported catalyst, and metallocene-supported catalyst prepared by the method | |
| CN105473601B (en) | Metallocene compound, comprising its carbon monoxide-olefin polymeric and using it prepare the method for olefin polymer | |
| EP2087012B1 (en) | Supported catalysts for olefin polymerization using transition metal compound having phenylene-bridge, method for preparing the same, and method for preparing polyolefin using the same | |
| KR101619396B1 (en) | Novel metallocene compound, Catalyst composition comprising the same, and Method for preparing olefin-based polymers using the same | |
| CN111116807B (en) | Preparation method of olefin-olefin alcohol copolymer | |
| CA2364011C (en) | Metallocene compounds and their use for olefin polymerization | |
| CN106795229B (en) | Metallocene-supported catalyst and method for preparing polyolefin using the same | |
| CN111909196A (en) | IVB group-containing bimetallic complex catalyst and preparation method and application thereof | |
| CN112778350B (en) | [ OONN ] tetradentate fourth subgroup metal complex, preparation method and application | |
| CN106661072A (en) | Metallocene compound, catalyst composition comprising same, and method for preparing olefin-based polymer using same | |
| KR101485567B1 (en) | Method for preparing supported metallocene catalyst, and supported metallocene catalyst using the same | |
| CN113039218A (en) | Supported catalyst for propylene polymerization and preparation method of polypropylene resin using the same | |
| KR102089057B1 (en) | Transition metal compound, catalyst composition comprising the same, and method for preparing olefin polymer using the same | |
| CN111662403A (en) | Cascade catalytic system and method for preparing LLDPE (Linear Low Density polyethylene) by using same | |
| CN1371924A (en) | High molecular nickel zirconium double activity center olefines polymerizing catalyst | |
| CN100590135C (en) | Neutral non-bridged combined metal chromium catalyst and its use | |
| CN1164625C (en) | High molecular 'after cyclopentadiene' alpha-diimine nickel base olefine polymerization catlayst | |
| CN111689997B (en) | Metal complex, preparation method and application thereof | |
| CN1132856C (en) | Catalyst for polymerizing semi-metallocene with olefin and its preparing process and application | |
| CN112745428A (en) | Preparation method of olefin-olefin alcohol copolymer | |
| CN112745427B (en) | Method for preparing olefin-olefin alcohol copolymer | |
| CN1208339C (en) | Single metallocene catalyst with naphthalene ring ligand and its prepn | |
| CN113754818B (en) | Method for producing olefin-olefin alcohol copolymer and olefin-olefin alcohol copolymer | |
| CN112608336B (en) | Quinoline diamine-containing fourth subgroup metal complex and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |