CN101864010B - Bimetallic catalyst precursor and application thereof to olefin polymerization or copolymerization - Google Patents
Bimetallic catalyst precursor and application thereof to olefin polymerization or copolymerization Download PDFInfo
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Abstract
The invention discloses a bimetallic catalyst precursor for catalyzing olefin to polymerize or copolymerize and belongs to the field of olefin coordination polymerization. The catalyst precursor is based on a salicvlaldimine ligand and an IV group transition metal. Compared with a monometallic catalyst, with the synergistic effect of bimetals, a catalyst consisting of the precursor and alkyl aluminum has higher activity when used for catalyzing the olefin to homopolymerize or copolymerize; particularly, the activity of the catalyst can reach 5.2*104g/mol<-1>h<-1> at the ethylene pressure of 1atm when used for catalyzing 1,5-hexadiene to be copolymerized with the ethylene; and in addition, the catalyst has higher ratio of inducing a comonomer into a polymer.
Description
Technical field
The invention belongs to the olefin coordination polymerization field, relate to the synthetic of a kind of bimetallic catalyst precursor and reach by its catalyzer of forming in the application aspect catalysis in olefine polymerization and the copolymerization.Specifically, synthesize a kind of dinuclear catalyst precursor of the IV group 4 transition metal based on the salicylic alidehyde imine part, used the copolymerization of catalyzed ethylene homopolymerization and ethene and substituted olefine effectively of catalyzer that this precursor and alkylaluminoxane form.
Background technology
For many years, the functionalization research of alkene is the focus of research always, functional polyolefin synthetic mainly is to obtain by conventional alkene (as ethene, propylene etc.) and functionalization alkene (claim the polar olefin monomer again, as methyl acrylate, vinyl acetate) copolymerization.Such polyolefine has various types of organo-functional group, makes polyolefinic chemically modified become on the one hand and is more prone to; All playing crucial active effect (Prog.Polym.Sci.1989,14,811) aspect the polyolefinic crystallinity of adjustment, intensity, fastness to rubbing, dyeability and the surface properties on the other hand.Therefore, the polyolefine of functionalization has a very application prospects industrial.
With Ziegler-Natta catalyst and metallocene catalyst is the development that the polycoordination of representative has promoted polyolefin industry, and be tending towards ripe gradually, nowadays, utilize such catalyzer can accurately control the taxis (Chem.Rev.2000 of polypropylene-base substituted olefine, 100,1223).But, because the polar olefin monomer contains electron rich heteroatoms such as aerobic, nitrogen and carbonyl, hydroxyl isopolarity group, these factors make metallocene catalyst that deactivation phenomenom take place when catalysis polar olefin monomer polymerization, cause polymerization termination (Chem.Rev.2000,100,1479).In order to address this problem, non-metallocene catalyst becomes the focus of polycoordination area research gradually.
In the research of non-metallocene catalyst, caused that based on the transition-metal catalyst of salicylic alidehyde imine part people pay close attention to greatly.Such catalyzer has good olefin catalytic activity, and for example: salicylic alidehyde imine closes nickel catalyzator and changed the situation that nickel catalyzator in the past can only obtain oligomer, the polyethylene (Science 2000,287,460) that obtained having certain degree of branching; And salicylic alidehyde imine close titanium catalyst can highly active catalysis synthesizing polyethylene, homopolymer (J.Am.Chem.Soc.2001,123,5134 such as polypropylene; J.Am.Chem.Soc.2002,124,3327), and can realize ethene and have the olefinic polymerization of functional group to have only 3% but obtain in the polymkeric substance ratio of comonomer, can not regulate and control the ratio (J.Am.Chem.Soc.2008 of comonomer in polymkeric substance effectively, 130,17636).
Can solve this difficult problem and have synergistic catalyzer.Studies show that, above the metal center of Brookhart type catalyst 3.8
The place introduces after the pyridine ring, uses promotor aluminium diethyl monochloride (AlEt
2Cl) can increase substantially the vinyl polymerization effect of this catalyzer, this is because AlEt
2Cl can form bridged bond between nitrogen-atoms and palladium (Pd) atom, thereby has suppressed the elimination (J.Am.Chem.Soc.2008,130,7538) of β-H.Have synergistic zirconocene catalysts and utilize, compare, not only can improve the polymerization activity of ethene, can also improve the ratio (PNAS.2006,103,15295) of comonomer in polymkeric substance with single zirconium metal catalyzer.
Summary of the invention
The present invention proposes a kind of based on the catalysis in olefine polymerization of salicylic alidehyde imine part or the bimetallic catalyst precursor and the catalyzer of copolymerization.
Technical scheme of the present invention is:
A kind of catalyst precursor is based on the bimetallic catalyst of the IV group 4 transition metal of salicylic alidehyde imine part, and its general structure is shown in I:
In the described formula I general structure, R is hydrogen atom or is the straight or branched alkyl of carbonatoms for (1-20) that preferred the total number of carbon atoms is the straight or branched alkyl of 4-12, most preferably tertiary butyl;
M is a metal, and described metal is selected from a kind of in IV group 4 transition metal titanium (Ti), zirconium (Zr), the hafnium (Hf), preferred titanium and zirconium; Ar
FFor containing the aryl of fluorine atom, described aryl is a pentafluorophenyl group, 2-fluorophenyl, 2,4 difluorobenzene base, 4-fluoro-3-chloro-phenyl-or 4-chloro-2,3,5,6-tetrafluoro phenyl, preferred pentafluorophenyl group.
Compound shown in the above-mentioned formula I general structure, metal catalyst shown in preferred formula II or the formula III,
(formula II) (formula III)
Wherein, the preferred R of formula I general structure is a tertiary butyl, and M is a titanium, Ar
FFor pentafluorophenyl group obtains formula II;
The preferred R of formula I general structure is a hydrogen, and M is a zirconium, Ar
FFor pentafluorophenyl group obtains formula III;
The invention provides the method for compound shown in the above-mentioned formula I general structure of preparation, comprise the steps;
1) under the condition of palladium catalyst, compound shown in the formula IV and 3-tertiary butyl-5-bromosalicylaldehyde are carried out the Suzuki linked reaction in organic solvent, obtain compound shown in the formula V, most preferably tertiary butyl (formula IV, formula V see accompanying drawing);
In the general structure, R is hydrogen atom or is the straight or branched alkyl of carbonatoms for (1-20) that preferred the total number of carbon atoms is the straight or branched alkyl of 4-12, most preferably tertiary butyl shown in the formula IV;
In the general structure, R is hydrogen atom or is the straight or branched alkyl of carbonatoms for (1-20) that preferred the total number of carbon atoms is the straight or branched alkyl of 4-12, most preferably tertiary butyl shown in the formula V;
2) under the condition that tosic acid exists, with compound shown in the described formula V in organic solvent with the fluoro aniline condensation, obtain compound shown in the formula VI;
In the general structure, R is hydrogen atom or is the straight or branched alkyl of carbonatoms for (1-20) that preferred the total number of carbon atoms is the straight or branched alkyl of 4-12, most preferably tertiary butyl shown in the formula V;
In the general structure, R is hydrogen atom or is the straight or branched alkyl of carbonatoms for (1-20) that preferred the total number of carbon atoms is the straight or branched alkyl of 4-12, most preferably tertiary butyl shown in the formula VI;
Shown in the formula VI in the general structure, Ar
FFor containing the aryl of fluorine atom, described aryl is a pentafluorophenyl group, 2-fluorophenyl, 2,4 difluorobenzene base, 4-fluoro-3-chloro-phenyl-or 4-chloro-2,3,5,6-tetrafluoro phenyl, preferred pentafluorophenyl group;
3) compound shown in the described formula VI and the 4th group 4 transition metal muriate with tetrahydrofuran (THF) are reacted in organic solvent, obtain bimetallic catalyst precursor I.
In the general structure, R is hydrogen atom or is the straight or branched alkyl of carbonatoms for (1-20) that preferred the total number of carbon atoms is the straight or branched alkyl of 4-12, most preferably tertiary butyl shown in the formula VI;
Shown in the formula VI in the general structure, Ar
FFor containing the aryl of fluorine atom, described aryl is a pentafluorophenyl group, 2-fluorophenyl, 2,4 difluorobenzene base, 4-fluoro-3-chloro-phenyl-or 4-chloro-2,3,5,6-tetrafluoro phenyl, preferred pentafluorophenyl group;
M is a metal, and described metal is selected from IV group 4 transition metal titanium, zirconium, a kind of in the hafnium.
In the step 1) of this method, described palladium catalyst is a kind of in tetrakis triphenylphosphine palladium, two (triphenylphosphine) Palladous chloride or the palladium;
In described step 1)-step 3), described organic solvent is tetrahydrofuran (THF), toluene, N, dinethylformamide, 1, a kind of in 4-dioxane or the methylene dichloride; The mol ratio of compound shown in the described formula IV, 3-tertiary butyl-5-bromosalicylaldehyde and described palladium catalyst is 1: (2.5-5): (0.03-0.1), and preferred 1: 3: 0.05; In the described Suzuki linked reaction, temperature is (60-100) ℃, and preferred 80 ℃, the time is (6-24) hour, preferred 12 hours;
Described step 2) in, the mol ratio of compound shown in the described formula V, contain fluorine atoms aniline and tosic acid is 1: (2-4): 0.001, and preferred 1: 3: 0.001; Temperature of reaction is (130-160) ℃, and preferred 150 ℃, the time is (8-24) hour, preferred 16 hours;
In the described step 3), compound shown in the described formula VI is 1 with the muriatic mol ratio of the 4th group 4 transition metal with tetrahydrofuran (THF): (1.8-2.2), and preferred 1: 2; In the described reaction, temperature is (0-40) ℃, and preferred 20 ℃, the time is (6-24) hour, preferred 12 hours.
The invention provides the catalyzer of being made up of above-mentioned bimetallic catalyst precursor (metal catalyst I), this catalyzer is made up of metal catalyst I and poly-aikyiaiurnirsoxan beta, and both mol ratios are 1: (200-2000), and preferred 1: (200-600).Ethene is polymerization reaction take place under the effect of this catalyzer, and described polymerization temperature is (0-70) ℃, preferred (30-50) ℃.
The general formula of above-mentioned poly-aikyiaiurnirsoxan beta is:
R is methyl or isobutyl-in the formula.Should poly-aikyiaiurnirsoxan beta can have straight chain, side chain or ring texture, as methylaluminoxane.
The above-mentioned catalyst system catalysis C that the present invention uses
4-C
10α substituted olefine or C
4-C
10Diolefine and the copolymerization of ethene, can prepare C
4-C
10α substituted olefine and ethylene copolymer or C
4-C
10Diolefine and ethylene copolymer.
Polyreaction of the present invention can be carried out in inert solvent.Solvent for use can be an aromatic hydrocarbons, benzene for example, toluene.
Compared with the prior art, the present invention has following high catalytic efficiency:
The single-metal reforming catalyst close with structure compared, bimetallic catalyst is when catalyzed ethylene homopolymerization or ethene and substituted olefine copolymerization, and polymerization activity is higher, particularly in catalysis 1, when 5-hexadiene and ethylene copolymer, activity can reach 5.2 * 10 under the 1atm ethylene pressure
4Gmol
-1H
-1And when catalyzed ethylene and substituted olefine copolymerization, the ratio of introducing comonomer in the resulting polymkeric substance is also higher.
Description of drawings
Fig. 1 is the general structure of bimetallic catalyst precursor of the present invention;
Fig. 2 is the preparation flow synoptic diagram of bimetallic catalyst precursor of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail:
The preparation of bimetallic catalyst precursor shown in the formula II
With 4,5-two bromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene is a starting raw material, under the condition that palladium catalyst exists with 3-tertiary butyl-5-(4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-replaces) coupling obtains 5 to salicylic aldehyde through Suzuki, 5 '-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-two replaces) two (3-tertiary butyl salicylic aldehydes).Then under the catalysis of tosic acid, with the condensation of penta fluoro benzene amine obtain (E)-4,4 '-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-two replaces) two (3-tertiary butyls-(E)-salicylidene penta fluoro benzene amine).In methylene dichloride, obtain bimetallic catalyst precursor II again with two (tetrahydrofuran (THF)) titanium tetrachloride reaction.As shown in Figure 2, concrete synthesis step is as follows:
1) preparation 5,5 '-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-two replaces) two (3-tertiary butyl salicylic aldehydes):
With 4; 5-two bromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene (2.18g; 4.5mmol); 3-tertiary butyl-5-(4,4,5; 5-tetramethyl--1; 3,2-two oxa-s borine-2-replaces) and salicylic aldehyde (3.02g, 10.0mmol); anhydrous sodium carbonate (2.41g; 23mmol), (0.52g 0.45mmol) places reaction flask to four (triphenyl phosphorus) palladium; vacuumize logical nitrogen three times; and under nitrogen protection, add the tetrahydrofuran (THF) 40ml that removed oxygen, and removing the water 10ml of oxygen, 18h refluxes under 80 ℃ of conditions.After reaction finished, separatory was adjusted to 5-6 with the pH value of water, with the anhydrous diethyl ether extraction of 10ml three times, merged organic phase.Use isopyknic saturated aqueous ammonium chloride and isopyknic saturated common salt water washing organic phase more successively.Organic phase is spin-dried for behind anhydrous sodium sulfate drying, and silicagel column separates, and is that the eluent of methylene dichloride/sherwood oil of 1/3 separates and obtains light yellow product with volume ratio.Productive rate: 82%.
1H?NMR(CDCl
3，300M)：11.61(s，2H，OH)，9.23(s，2H，CHO)，7.59(d，2H，J＝2.4Hz，ArH)，7.46(d，2H，J＝2.4Hz，ArH)，7.33(d，2H，J＝2.4Hz，ArH)，7.17(d，2H，J＝2.4Hz，ArH)，1.77(s，6H，C(CH
3)
2)，1.38(s，9H，C(CH
3)
3)，1.33(s，9H，C(CH
3)
3)。
13C?NMR(CDCl
3，300M)：196.0，159.8，145.7，144.9，137.9，135.5，132.9，129.9，129.1，127.6，125.9，122.2，120.1，34.9，34.8，34.5，32.8，31.5，29.2。El-MS?calcd?for?C
45H
54O5m/z：674，Found：674(M
+)。
2) preparation (E)-4,4 '-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-two replaces) two (3-tertiary butyls-(E)-salicylidene penta fluoro benzene amine):
With 5,5 '-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-two replaces) two (3-tertiary butyl salicylic aldehyde) (2.00g, 2.96mmol), pentafluorophenyl group (1.08g, 5.92mmol) (0.01g 0.05mmol) places round-bottomed flask with tosic acid, with the dissolving of 50ml toluene, and be heated to 150 ℃ of backflow 24h.After reaction finishes, earlier with isopyknic deionized water wash twice, again with isopyknic anhydrous chlorides of rase sodium solution washing organic phase.Organic phase is spin-dried for behind anhydrous sodium sulfate drying, and silicagel column separates, and is that the eluent separation obtains yellow product with the sherwood oil.Productive rate: 85%.
1H?NMR(CDCl
3，300M)：11.61(s，2H，OH)，9.23(s，2H，CHO)，7.59(d，2H，J＝2.4Hz，ArH)，7.46(d，2H，J＝2.4Hz，ArH)，7.33(d，2H，J＝2.4Hz，ArH)，7.17(d，2H，J＝2.4Hz，ArH)，1.77(s，6H，C(CH
3)
2)，1.38(s，9H，C(CH
3)
3)，1.33(s，9H，C(CH
3)
3)。
13C?NMR(CDCl
3，300M)：170.2，159.9，145.7，145.1，141.3(m，
1J
C-F＝243.9Hz，Ar
FC-F)，138.9(m，
1J
C-F＝250.8Hz，Ar
FC-F)，138.0(m，
1J
C-F＝240.7Hz，Ar
FC-F)，137.8，134.3，132.6，129.9，129.0，127.7，126.3，123.1(m，Ar
FC-F)，122.1，118.2，34.9，34.9，34.6，33.0，31.6，29.1。MALDl-TOF-MS?calcd?for?C
45H
54O5m/z：1004.40，Found：1005.41(M+H
+)。Anal?Calcd?forC
45H
54O5：C，68.12；H，5.42；N，2.79。Found：C，68.17；H，5.48；N，2.83。
3) precursor of bimetal titanium catalyst shown in the preparation formula II:
With (E)-4,4 '-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-two replaces) two (the 3-tertiary butyl-(E)-salicylidene penta fluoro benzene amine) (0.80g, dichloromethane solution 0.80mmol) slowly join two (tetrahydrofuran (THF)) titanium tetrachloride (0.544g under-78 ℃, 1.64mmol) dichloromethane solution in, return to room temperature through behind the 6h, and heat 8h down at 40 ℃, reaction finishes.Solvent is drained on vacuum line, and remaining solid obtains the sorrel solid, productive rate: 82% with methylene dichloride and normal hexane recrystallization.
1H?NMR(CDCl
3，300M)：8.56(br?s，2H，CH＝N)，7.84(br?s，2H，ArH)，7.59(br?s，2H，ArH)，7.52(br?s，2H，ArH)，7.16(br?s，2H，ArH)，4.27(br?s，4H，O(CH
2)
2)，2.02(br?s，4H，CH
2)，1.81(s，6H，C(CH
3)
2)，1.39(s，9H，C(CH
3)
3)，1.17(s，9H，C(CH
3)
3)。
13C?NMR(CDCl
3，300M)：173.4，161.8，146.2，144.3，141.2(m，
1J
C-F＝186.2Hz，Ar
FC-F)，140.2(m，
1J
C-F＝195.0Hz，Ar
FC-F)，138.8，137.6(m，
1J
C-F＝187.5Hz，Ar
FC-F)，137.3，135.0，132.8，129.9，128.4，127.3(m，Ar
FC-F)，126.3，125.5，123.7，77.2，34.7，34.6，33.8，31.5，29.8。Anal?Calcd?for?C
45H
54O
5：C，53.63；H，4.71；N，1.92。Found：C，53.51；H，4.77；N，2.01。
4) bimetal Zr catalyst precursor shown in the preparation formula III:
With (E)-4,4 '-(9,9-dimethyl-9H-xanthene-4,5-two replaces) two (the 3-tertiary butyl-(E)-salicylidene penta fluoro benzene amine) (0.50g, 0.56mmol) dichloromethane solution under-78 ℃, slowly join two (tetrahydrofuran (THF)) zirconium tetrachlorides (0.42g in dichloromethane solution 1.12mmol), return to room temperature through behind the 6h, and under 40 ℃, heat 8h, reaction finishes.Solvent is drained remaining solid methylene dichloride and normal hexane recrystallization on vacuum line.
Poly synthetic: as will to vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, through the toluene 23.2ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 25 ℃ of reaction 10min, add alcoholic acid souring soln termination reaction again, obtain polymkeric substance 0.054g, active 4.1 * 10
4Gmol
-1H
-1
It is 137 ℃ that DSC records fusing point; GPC records poly M
wBe 5.1 * 10
5, M
w/ M
nBe 15.2.
Poly synthetic: as will to vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, through the toluene 23.2ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 25 ℃ of reaction 5.0min, add alcoholic acid souring soln termination reaction again, obtain polymkeric substance 0.027g, active 4.1 * 10
4Gmol
-1H
-1
It is 136 ℃ that DSC records fusing point; GPC records poly M
wBe 4.0 * 10
5, M
w/ M
nBe 7.7.
Embodiment 4
Poly synthetic: as will to vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, through the toluene 23.2ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 25 ℃ of reaction 7.5min, add alcoholic acid souring soln termination reaction again, obtain polymkeric substance 0.037g, active 3.8 * 10
4Gmol
-1H
-1
It is 139 ℃ that DSC records fusing point; GPC records poly M
wBe 6.2 * 10
5, M
w/ M
nBe 37.7.
Embodiment 5
Poly synthetic: as will to vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, through the toluene 23.2ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 25 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction, obtain polymkeric substance 0.258g, active 3.3 * 10
4Gmol
-1H
-1
It is 138 ℃ that DSC records fusing point.
Embodiment 6
Poly synthetic: as will to vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, through the toluene 23.2ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 0 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction again, obtain polymkeric substance 0.186g, active 2.4 * 10
4Gmol
-1H
-1
It is 135 ℃ that DSC records fusing point.
Embodiment 7
Poly synthetic: as will to vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, through the toluene 23.2ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feed pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 40 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction, obtain polymkeric substance 0.145g, active 1.9 * 10
4Gmol
-1H
-1
It is 136 ℃ that DSC records fusing point.
Embodiment 8
Poly synthetic: as will to vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, through the toluene 23.2ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 60 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction, obtain polymkeric substance 0.136g, active 1.8 * 10
4Gmol
-1H
-1
It is 135 ℃ that DSC records fusing point.
Embodiment 9
Poly synthetic: as will to vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 3.4ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, through the toluene 26.6ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 25 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction, obtain polymkeric substance 0.260g, active 3.3 * 10
4Gmol
-1H
-1
It is 135 ℃ that DSC records fusing point.
Embodiment 10
Poly synthetic: as will to vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 13.6ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, through the toluene 16.4ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 25 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction, obtain polymkeric substance 0.259g, active 3.3 * 10
4Gmol
-1H
-1
It is 136 ℃ that DSC records fusing point.
The vinyl polymerization experimental result sees Table 1
*P
ethylene＝1atm，V
tol＝50ml
Table 1: vinyl polymerization data
Embodiment 11
Synthesizing of ethene and 1-hexene copolymer: will vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, 1-hexene 4.5ml, through the toluene 18.7ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 25 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction, obtain polymkeric substance 0.068g, active 0.9 * 10
4Gmol
-1H
-1
It is 119 ℃ that DSC records fusing point; GPC records poly M
wBe 1.7 * 10
5, M
w/ M
nBe 13.9.
Embodiment 12
Synthesizing of ethene and 1-hexene copolymer: will vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, 1-hexene 1.2ml, through the toluene 22ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 25 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction, obtain polymkeric substance 0.117g, active 1.5 * 10
4Gmol
-1H
-1
It is 123 ℃ that DSC records fusing point; GPC records poly M
wBe 2.6 * 10
5, M
w/ M
nBe 13.9.
Embodiment 13
Synthesizing of ethene and 1-hexene copolymer: will vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, 1-hexene 6.9ml, through the toluene 16.3ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 25 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction, obtain polymkeric substance 0.074g, active 1.0 * 10
4Gmol
-1H
-1
It is 115 ℃ that DSC records fusing point; GPC records poly M
wBe 1.7 * 10
5, M
w/ M
nBe 10.3.
Embodiment 14
Synthesizing of ethene and 1-hexene copolymer: will vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, 1-hexene 3.1ml, through the toluene 20.1ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 40 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction, obtain polymkeric substance 0.202g, active 2.5 * 10
4Gmol
-1H
-1
It is 114 ℃ that DSC records fusing point; It is 4.7% that nuclear-magnetism carbon spectrum records 1-hexene introducing ratio.
Embodiment 15:
Synthesizing of ethene and 1-octene copolymer: will vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, 1-octene 5.6ml, through the toluene 17.6ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 40 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction, obtain polymkeric substance 0.068g, active 0.9 * 10
4Gmol
-1H
-1
It is 12.9% that nuclear-magnetism carbon spectrum records 1-octene introducing ratio.
Embodiment 16
Synthesizing of ethene and 1-octene copolymer: will vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, 1-octene 3.9ml, through the toluene 18.6ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 40 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction, obtain polymkeric substance 0.261g, active 3.3 * 10
4Gmol
-1H
-1
It is 114 ℃ that DSC records fusing point; It is 3.0% that nuclear-magnetism carbon spectrum records 1-octene introducing ratio.
Embodiment 17
Ethene and 1, synthesizing of 5-hexadiene multipolymer: will vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, 1,5-hexadiene 4.3ml is through the toluene 18.9ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 40 ℃ of reaction 1h, add alcoholic acid souring soln termination reaction again, obtain polymkeric substance 0.214g, active 2.6 * 10
4Gmol
-1H
-1
It is 7.6% that nuclear-magnetism carbon spectrum records 1-octene introducing ratio.
Embodiment 18
Ethene and 1, synthesizing of 5-hexadiene multipolymer: will vacuumize logical nitrogen through the 250ml polymerization bottle behind the heat drying twice, vacuumize the back again and feed ethylene gas, the toluene solution 6.8ml (concentration is 1.47mol/l) that adds methylaluminoxane (MAO) then successively, 1,5-hexadiene 3.0ml is through the toluene 20.2ml that anhydrous and oxygen-free is handled, the toluene solution 20ml (0.55mg/ml) of metal catalyst II.Feeding pressure under magnetic agitation is the ethene of 1atm, and under this pressure in 40 ℃ of reaction 30min, add alcoholic acid souring soln termination reaction again, obtain polymkeric substance 0.211g, active 5.2 * 10
4Gmol
-1H
-1
It is 120 ℃ that DSC records fusing point
Ethene and substituted olefine polymeric experimental result see Table 2 (contrasting with single-metal reforming catalyst)
*P
ethylene＝1atm，V
tol＝50ml，C
comonomer＝0.5mol/L
Table 2: ethene and substituted olefine aggregated data
Also as can be seen, bimetallic catalyst is when catalysis in olefine polymerization or copolymerization from table, and the ratio of polymerization activity and introducing comonomer will be higher than single-metal reforming catalyst, thereby has also proved the validity with synergy catalyzer that we are designed.
More than by specific embodiment described catalyzed ethylene polymerization provided by the present invention or copolymerization bimetallic catalyst precursor and by its catalyzer of forming, those skilled in the art is to be understood that, in the scope that does not break away from essence of the present invention, can make certain conversion or modification to the present invention; Be not limited to disclosed content among the embodiment.
Claims (9)
1. a catalyst precursor is characterized in that, is based on the bimetallic catalyst that salicylic alidehyde imine is the IV group 4 transition metal of part, its structure as shown in Equation 1:
Among the described formula I, R is a hydrogen atom or for carbonatoms is the straight or branched alkyl of 1-20, Ar
FFor containing the fluorine atom aryl, M is an IV group 4 transition metal titanium, zirconium, a kind of in the hafnium.
2. catalyst precursor as claimed in claim 1 is characterized in that, the described fluorine atom aryl that contains is a pentafluorophenyl group, 2-fluorophenyl, 2,4 difluorobenzene base, 4-fluoro-3-chloro-phenyl-or 4-chloro-2,3,5,6-tetrafluoro phenyl.
3. the preparation method of a catalyst precursor is characterized in that,
1) under the condition of palladium catalyst, with 4,5-two bromo-2,7-dialkyl group-9,9-dimethyl-9H-xanthene and 3-tertiary butyl-5-(4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-replacement) salicylic aldehyde carries out the Suzuki linked reaction in organic solvent, obtain formula 5,5 '-(2,7-dialkyl group-9,9-dimethyl-9H-xanthene-4,5-two replaces) two (3-tertiary butyl salicylic aldehydes);
2) under the condition of tosic acid, with 5,5 '-(2,7-dialkyl group-9,9-dimethyl-9H-xanthene-4,5-two replaces) two (3-tertiary butyl salicylic aldehydes) in organic solvent with the aniline condensation that has fluorine atom, obtain (E)-4,4 '-(2,7-dialkyl group-9,9-dimethyl-9H-xanthene-4,5-two replaces) two (the 3-tertiary butyl-(E)-salicylidene fluoro aniline);
3) with (E)-4,4 '-(2,7-dialkyl group-9,9-dimethyl-9H-xanthene-4,5-two replaces) two (the 3-tertiary butyl-(E)-salicylidene fluoro aniline) react in organic solvent with the transition metal chloride that has tetrahydrofuran (THF), obtain the bimetallic catalyst precursor shown in the formula I.
4. method as claimed in claim 3 is characterized in that, in the described Suzuki linked reaction, temperature is 60-100 ℃, and the time is 6-24 hour.
5. method as claimed in claim 3 is characterized in that, described step 2) in, 5,5 '-(2,7-dialkyl group-9,9-dimethyl-9H-xanthene-4,5-two replaces) mol ratio of two (3-tertiary butyl salicylic aldehydes), fluoro aniline and tosic acid is 1: 2-4: 0.001.
6. method as claimed in claim 3, it is characterized in that, in the described step 3), (E)-4,4 '-(2,7-dialkyl group-9,9-dimethyl-9H-xanthene-4,5-two replaces) two (3-tertiary butyls-(E)-salicylidene fluoro aniline) be 1 with the mol ratio that has the transition metal chloride of tetrahydrofuran (THF): 1.8-2.2.
7. method as claimed in claim 3 is characterized in that, in described step 1)-step 3), described organic solvent is tetrahydrofuran (THF), toluene, N, dinethylformamide, 1, a kind of in 4-dioxane or the methylene dichloride.
8. a catalyzer that is used for catalysis in olefine polymerization or copolymerization is characterized in that, is made up of described catalyst precursor of claim 1 and poly-aikyiaiurnirsoxan beta, and the general formula of poly-aikyiaiurnirsoxan beta is:
R is methyl or isobutyl-in the formula, and this poly-aikyiaiurnirsoxan beta can have straight chain, side chain or ring texture, and both mol ratios are 1: 200-2000.
9. as the polymerization of catalyzer catalyzed alkene in aromatic solvent as described in the claim 8 and the application in the copolymerization, wherein: alkene is ethene, C
4-C
10α substituted olefine or C
4-C
10Diolefine in one or both, aromatic solvent is benzene or toluene.
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| CN102358759B (en) * | 2011-07-27 | 2013-03-13 | 北京大学 | Nickel metal catalyst precursor with hydrogen bond binding sites, synthesis method, and application thereof |
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| CN107098992B (en) * | 2017-05-15 | 2019-06-07 | 北京大学 | Cyclic annular multicore salicylic alidehyde imine nickel-metal catalyst precursor and its preparation and application |
| CN107298727B (en) * | 2017-06-28 | 2019-07-26 | 青岛科技大学 | A kind of preparation and application of double salicylaldehyde imines-anthracene bimetallic titanium catalyst |
| CN110272513B (en) * | 2018-03-15 | 2021-10-19 | 中国石油化工股份有限公司 | Post-metallocene catalyst precursor, preparation method thereof, catalyst, application thereof and ethylene homopolymerization method |
| CN110272515B (en) * | 2018-03-15 | 2021-10-19 | 中国石油化工股份有限公司 | Process for the preparation of ethylene copolymers |
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