CN1995044A - Tetradentate IV B transition metal catalyst, preparation method and uses - Google Patents
Tetradentate IV B transition metal catalyst, preparation method and uses Download PDFInfo
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Abstract
The invention discloses a quadridentate IVB transition metal catalyst, making method and application in the olefin polymerizing course with structure in the picture, wherein R1 is substituted base on the benzene ring with the number at 1-4; R1 is hydrogen, C1-6 alkyl, isopropyl, tert-butyl, phenyl, cumenyl, methoxy, nitrate or halogen; R2 is hydrogen or C1-3 alkyl; M is IVB metal; X is halogen; Y is bridging group; Z is as formula or benzene ring with substituted benzene group.
Description
Technical field
The present invention relates to a kind of catalyzer, relate in particular to a kind of when olefinic polymerization, have highly active a kind of four tooth IVB group 4 transition metal catalyzer, preparation method and application thereof.
Background technology
Modern polymerization catalyzed, originate from metallocene catalyst and to the related understanding of structure with the polymer properties of part.The focus of current olefin polymerization catalysis research is: rear transition metal mainly is the research of VIII group element compound, and wherein the nickel compound of Schiff's base has the high reactivity of single component catalyzed ethylene; The research of early transition metal compound concentrates on group vib, and wherein Schiff's base IV family title complex (FI catalyzer) is the highest catalyzer of catalytic activity up to now, is the catalyzer of new generation after Ziegler-Natta catalyst and metallocene catalyst.Bidentate [N, O] the IVB titanium is that the FI olefin polymerization catalysis is compared with metallocene catalyst, the FI catalyzer have catalysis in olefine polymerization high reactivity, obtain high molecular weight polymers, living polymerization, be easy to series of advantages such as preparation, thereby cause people's extensive attention.
With the tetradentate schiff base be the compound of part in the development of the coordination chemistry relevant with katalysis in occupation of very important role.Though synthetic, the structure and the catalytic performance of this type of title complex of rear transition metal are widely studied, seldom for the chemical reaction of titanium, zirconium four tooth Schiff bases complex compounds and Catalytic Performance report.Tetradentate schiff base class part contains can two Sauerstoffatoms of coordinate and two nitrogen-atoms, and provide enough solid spaces by the intermediary carbochain for metal titanium ion and its coordination.Chinese patent 03149936.8 discloses a kind of double-core titanium polyolefin catalyzer, this catalyzer adopts the diphenylamine compound and the carbonyl pyridine compound condensation reaction of bridging to make ligand compound, make the catalyzer of dual-core architecture again with transistion metal compound, under the effect of MAO promotor, the catalyzer that can be used as ethylene polymerization, but catalyst activity and polymericular weight are all on the low side.
Summary of the invention
A kind of four tooth IVB group 4 transition metal catalyzer, preparation method and application thereof, purpose are provided is to improve catalyst activity and polymericular weight in order to solve the problems of the technologies described above in the present invention.
Another object of the present invention provides a kind of four application of tooth IVB group 4 transition metal catalyzer in olefinic polymerization.
A kind of four tooth IVB group 4 transition metal catalyzer of the present invention, structure is as follows:
R in the formula
1Be the substituting group on the phenyl ring, the replacement radix on each phenyl ring is 1～4, R
1Be hydrogen, C
1～C
6Alkyl, sec.-propyl, tertiary butyl, phenyl, cumyl, methoxyl group, nitroxyl or halogen; R
2Be hydrogen or C
1～C
3Alkyl; M is an IVB family metal; X is a halogen; Y is a bridged group; Z is
Or have a substituent phenyl ring.
Described substituent R
1Be positioned at 3～6 of phenyl ring.
Described halogen is a chlorine or bromine; M is titanium or zirconium.
Described Z is with substituent phenyl ring, and structure is as follows:
R wherein
3Be hydrogen, C
1～C
6Alkyl, sec.-propyl or tertiary butyl; R
4Be hydrogen, C
1～C
6Alkyl.
Described Y is-O-,-S-,-MeN-,-CH
2-,-MeCH-,-Me
2C-,-CH
2-Me
2C-CH
2-,-(Ph)
2C-,-(Me)
2Si-,-(Ph)
2Si-,-(Me)
2Ge-,-(Me)
2Sn-,-(Me)
2Si-O-Si (Me)
2-,-(Me)
2Si-MeN-Si (Me)
2-or-(Me)
2Si-
nBuN-Si (Me)
2-.
A kind of four tooth IVB group 4 transition metal Preparation of catalysts methods, it comprises the steps:
(1) under the anhydrous and oxygen-free condition, in alcoholic solvent, be catalyzer with the organic acid, with substituted salicylic aldehydes and bridging diamine compounds, carry out the Schiff's base condensation reaction by 2: 1 mol ratio down at 0～100 ℃, remove and desolvate, the gained solid drying is promptly got ligand compound with four toothings; (2) under the anhydrous and oxygen-free condition, in tetrahydrofuran solvent, the above-mentioned ligand compound that makes and basic metal, alkali metal compound or alkaline earth metal compound are reacted down at-40～60 ℃ by 1: 2 mol ratio, make basic metal or alkaline earth salt; (3) under the anhydrous and oxygen-free condition, in tetrahydrofuran solvent, will make basic metal or alkaline earth salt and MX
4Transition metal halide reacts down at-40～100 ℃ by 1: 1 mol ratio, removes tetrahydrofuran solvent, and resistates organic substance extraction, extract concentrate the back chromatography and get four tooth transition-metal catalysts.
Alcoholic solvent in described (1) step is methyl alcohol or ethanol, and organic acid is formic acid or acetate; (2) Bu basic metal is for receiving or potassium, and alkali metal compound is that butyllithium or hydrogenation are received, and alkaline earth metal compound is methylmagnesium-chloride or ethylmagnesium chloride; (3) Bu MX
4Transition metal halide is titanium tetrachloride or zirconium tetrachloride, and the organic solvent that is used for extracted residues is methylene dichloride or toluene, and concentration method adopts concentrating under reduced pressure or cryogenic freezing to concentrate, and the chromatography solvent is normal hexane or sherwood oil.
Described bridging diamine compounds structure is:
A kind of four application of tooth IVB group 4 transition metal catalyzer in olefinic polymerization, with four tooth IVB group 4 transition metal catalyzer is Primary Catalysts, with aluminum alkyls or aikyiaiurnirsoxan beta is promotor, in hexane, methylene dichloride or toluene solvant, make alkene under-25～100 ℃, 0.1～2MPa condition, carry out polyreaction; Primary Catalysts concentration is 0.1～1000 μ mol/L during reaction, in the promotor in Al and the Primary Catalysts mol ratio of metal be 10～3000: 1.
Described aluminum alkyls is triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium or tri-n-octylaluminium; Aikyiaiurnirsoxan beta is a methylaluminoxane or through the methylaluminoxane of triisobutyl aluminium modification.
Advantageous effect of the present invention:
The diamine compounds of catalyzer employing substituted salicylic aldehydes compounds of the present invention and bridging carries out the condensation reaction preparation and contains two [N, O] tetradentate schiff base class ligand compound, this part contains energy two Sauerstoffatoms of coordinate and two nitrogen-atoms, react the catalyzer that can prepare four toothings with transition metal, in this structure, the substituting group that connects on the imido grpup can provide enough solid spaces for part and metallic ion coordination.It under the methylaluminoxane effect highly active ethylene rolymerization catalyst.
Embodiment
Further specify the present invention below in conjunction with example, but scope of the present invention is not limited to these examples.
Embodiment 1: a kind of four tooth IVB group 4 transition metal catalyzer of the present invention describe with [two (salicylic aldehydes) contract 4,4 '-oxydianiline] titanium dichloride Preparation of catalysts.Comprise the steps:
(1) two (salicylic aldehyde) contract 4,4 '-preparation of oxydianiline part
Under anhydrous and oxygen-free nitrogen protection condition, salicylic aldehyde 0.01mol 20ml dissolve with methanol in the 100ml there-necked flask, 4 of 0.005mol, 4 '-diaminodiphenyl oxide is dissolved in 10ml methyl alcohol, slowly drops in the methanol solution of salicylic aldehyde, dropwises, splash into 2 formic acid, 40 ℃ of reaction 5h, stopped reaction filters, the filter residue methanol wash, part a: two (salicylic aldehydes) contract 4,4 '-oxydianiline, productive rate: 95%; FT-IR:3420 (OH), 1613 (C=N), 1250 (C-O);
(2) two (salicylic aldehydes) contract 4,4 '-preparation of oxydianiline part salt
Under anhydrous and oxygen-free nitrogen protection condition, in the 100ml there-necked flask two (salicylic aldehydes) contract 4,4 '-oxydianiline is with the dissolving of 20ml tetrahydrofuran (THF), is cooled to subzero 20 ℃, slowly adds the 0.0061mol sodium hydride under this temperature, rises to room temperature reaction 2h;
(3) preparation of [two (salicylic aldehydes) contract 4,4 '-oxydianiline] titanium dichloride
Under anhydrous and oxygen-free nitrogen protection condition, the sodium salt solution of part is transferred to constant pressure funnel; Under-40 ℃ of conditions, the 0.005mol titanium tetrachloride dissolves with the 10ml tetrahydrofuran (THF) in the 100ml there-necked flask, slowly drips the sodium salt solution of part, and 30min drips off, room temperature reaction 15h, stopped reaction, tetrahydrofuran (THF) is removed in decompression, adds the 20ml methylene dichloride in the resistates, migrate out supernatant liquid with steel pipe, behind the concentrating under reduced pressure, add the 10ml sherwood oil in the solution, separate out a large amount of solids; With petroleum ether twice, nitrogen drying, catalyst A: [two (salicylic aldehydes) contract 4,4 '-oxydianiline] titanium dichloride, productive rate 75%; Catalyst structure is as follows: FI-IR:1639 (C=N), 1247 (Ar-O), 735 (Ti-N), 505 (Ti-O).
Embodiment 2:[two (o-vanillin) contracts 4,4 '-oxydianiline] preparation of titanium dichloride
Method by (1) among the embodiment 1 step prepares part, and different is that the salicylic aldehyde that (1) goes on foot is replaced to o-vanillin, and alcoholic solvent is an ethanol, organic acid is an acetate, temperature of reaction is that 60 ℃ of reaction 4h get part b: two (o-vanillins) contract 4,4 '-oxydianiline, productive rate 98%; FI-IR:3423 (OH), 1614 (C=N), 1255 (Ar-O);
(2) preparation of [two (o-vanillins) contract 4,4 '-oxydianiline] titanium dichloride
Method by (2) among the embodiment 1, (3) step prepares catalyzer, and different is to replace part a and titanium tetrachloride reaction with part b, and subzero 40 ℃ of the temperature of reaction in the step (2) was reacted 4 hours, and basic metal is sodium; Subzero 20 ℃ of step (3) temperature of reaction was reacted 12 hours, catalyst B: [two (o-vanillins) contract 4,4 '-oxydianiline] titanium dichloride, productive rate 80%.Catalyst structure is as follows.FI-IR：1641(C＝N)、1249(Ar-O)、737(Ti-N)、508(Ti-O)。
Embodiment 3:[two (3-propyl group-5-cresotinic acid aldehyde) contracts 4,4 '-phenothiazine] preparation of titanium dichloride
(1) two (3-propyl group-5-cresotinic acid aldehyde) contract 4,4 '-preparation of phenothiazine part
Method by (1) among the embodiment 1 step prepares part, different is with (1) salicylic aldehyde and 4 in step, 4 '-diaminodiphenyl oxide replaces to 3-propyl group-5-cresotinic acid aldehyde and 4 respectively, 4 '-diaminodiphenyl sulfide, temperature of reaction is that 0 ℃ of reaction 10h gets part c: two (3-propyl group-5-cresotinic acid aldehyde) contract 4,4 '-phenothiazine, productive rate 90%; FI-IR:3420 (OH), 1616 (C=N), 1253 (Ar-S).
(2) preparation of [two (3-propyl group-5-cresotinic acid aldehyde) contract 4,4 '-phenothiazine] titanium dichloride
Method by (2) among the embodiment 1, (3) step prepares catalyzer, and different is to replace part a and titanium tetrachloride reaction with part c, and subzero 0 ℃ of the temperature of reaction in the step (2) was reacted 4 hours, and basic metal is potassium; Subzero 0 ℃ of step (3) temperature of reaction was reacted 8 hours, and the chromatography solvent is a normal hexane, catalyzer C:[two (3-propyl group-5-cresotinic acid aldehyde) contract 4,4 '-phenothiazine] titanium dichloride, productive rate 70%; Catalyst structure is as follows: FI-IR:1640 (C=N), 1247 (Ar-S), 738 (Ti-N), 508 (Ti-O).
Embodiment 4:[two (3-phenyl salicylic aldehyde) contracts 4,4 '-nitrogen-bridged-two (2, the 6-xylidine) of methyl] preparation of titanium dichloride
(1) two (3-phenyl salicylic aldehyde) contract 4,4 '-preparation of methyl nitrogen-bridged-two (2, the 6-xylidine) part
Method by (1) among the embodiment 1 step prepares part, different is with (1) salicylic aldehyde and 4 in step, 4 '-diaminodiphenyl oxide replaces to 3-phenyl salicylic aldehyde and 4 respectively, 4 '-methyl nitrogen-bridged-two (2, the 6-xylidine), temperature of reaction is that 80 ℃ of reaction 3h get part d: two (3-phenyl salicylic aldehydes) contract 4,4 '-methyl nitrogen-bridged-two (2, the 6-xylidine), productive rate 73%; FI-IR:3420 (OH), 1616 (C=N), 1260 (Ar-N);
(2) preparation of [two (3-phenyl salicylic aldehydes) contract 4,4 '-nitrogen-bridged-two (2, the 6-xylidine) of methyl] titanium dichloride
Method by (2) among the embodiment 1, (3) step prepares catalyzer, and different is to replace part a and titanium tetrachloride reaction with part d, and 20 ℃ of the temperature of reaction in the step (2) were reacted 4 hours, and alkali metal compound is a butyllithium; 0 ℃ of step (3) temperature of reaction was reacted 10 hours, and the organic solvent that is used for extracted residues is a toluene, cryogenic freezing concentrates to such an extent that catalyzer D:[two (3-phenyl salicylic aldehyde) contracts 4,4 '-nitrogen-bridged-two (2, the 6-xylidine) of methyl] titanium dichloride, productive rate 70%; Catalyst structure is as follows: FI-IR:1640 (C=N), 1251 (Ar-N), 738 (Ti-N), 508 (Ti-O).
Embodiment 5:[two (3-tertiary butyl salicylic aldehyde) contracts 4,4 '-methylene radical-two (2, the 6-diisopropyl aniline)] preparation of titanium dichloride
(1) two (3-tertiary butyl salicylic aldehyde) contract 4,4 '-preparation of methylene dianiline (MDA) part
Method by (1) among the embodiment 1 step prepares part, different is with (1) salicylic aldehyde and 4 in step, 4 '-diaminodiphenyl oxide replaces to 3-tertiary butyl salicylic aldehyde and 4 respectively, 4 '-methylene radical-two (2, the 6-diisopropyl aniline), temperature of reaction is that 100 ℃ of reaction 2h get part e: two (3-tertiary butyl salicylic aldehydes) contract 4,4 '-methylene radical-two (2, the 6-diisopropyl aniline), productive rate 81%; FI-IR:3420 (OH), 1616 (C=N), 1258 (Ar-C);
(2) preparation of [two (3-tertiary butyl salicylic aldehydes) contract 4,4 '-methylene radical-two (2, the 6-diisopropyl aniline)] titanium dichloride
Method by (2) among the embodiment 1, (3) step prepares catalyzer, and different is to replace part a and titanium tetrachloride reaction with part e, and 40 ℃ of the temperature of reaction in the step (2) were reacted 2 hours, and alkaline earth metal compound is a methylmagnesium-chloride; 40 ℃ of step (3) temperature of reaction were reacted 8 hours, catalyzer E:[two (3-tertiary butyl salicylic aldehyde) contract 4,4 '-methylene radical-two (2, the 6-diisopropyl aniline)] titanium dichloride, productive rate 78%; Catalyst structure is as follows: FI-IR:1640 (C=N), 1246 (Ar-C), 738 (Ti-N), 508 (Ti-O).
Embodiment 6:[two (3,5-diisopropylbenzyl salicylic aldehyde) contracts 4,4 '-dimethyl-silicon bridging pentanoic] preparation of titanium dichloride
(1) two (3,5-diisopropylbenzyl salicylic aldehyde) contract 4,4 '-preparation of dimethyl-silicon bridging pentanoic part
Method by embodiment 1 (1) step prepares part, different is with (1) salicylic aldehyde and 4 in step, 4 '-diaminodiphenyl oxide replaces to 3 respectively, 5-diisopropylbenzyl salicylic aldehyde and 4,4 '-dimethyl-silicon bridging pentanoic, get part f: two (3,5-diisopropylbenzyl salicylic aldehyde) contract 4,4 '-dimethyl-silicon bridging pentanoic, productive rate 87%; FI-IR:3420 (OH), 1616 (C=N), 1263 (Ar-Si);
(2) preparation of [two (3,5-diisopropylbenzyl salicylic aldehyde) contract 4,4 '-dimethyl-silicon bridging pentanoic] titanium dichloride
Method by (2) among the embodiment 1, (3) step prepares catalyzer, and different is to replace part a and titanium tetrachloride reaction with part f, and subzero 60 ℃ of the temperature of reaction in the step (2) was reacted 1 hour, and alkaline earth metal compound is an ethylmagnesium chloride; 80 ℃ of step (3) temperature of reaction were reacted 8 hours, catalyzer F:[two (3,5-diisopropylbenzyl salicylic aldehyde) contract 4,4 '-dimethyl-silicon bridging pentanoic] titanium dichloride, productive rate 76%; Catalyst structure is as follows: FI-IR:1640 (C=N), 1251 (Ar-Si), 738 (Ti-N), 508 (Ti-O).
Embodiment 7:[two (3-nitro-5-chloro salicylic aldehyde) contracts 4,4 '-the silica-based bridging pentanoic of silica] preparation of zirconium dichloride
(1) two (3-nitro-5-chloro salicylic aldehyde) contract 4,4 '-preparation of the silica-based bridging pentanoic of silica part
Method by (1) among the embodiment 1 step prepares part, different is with (1) salicylic aldehyde and 4 in step, 4 '-diaminodiphenyl oxide replaces to 3-nitro-5-chloro salicylic aldehyde and 4 respectively, 4 '-the silica-based bridging pentanoic of silica, get part g: two (3-nitros-5-chloro salicylic aldehyde) contract 4,4 '-the silica-based bridging pentanoic of silica, productive rate 91%; FI-IR:3420 (OH), 1616 (C=N), 1264 (Ar-Si);
(2) preparation of [two (3-nitros-5-chloro salicylic aldehyde) contract 4,4 '-the silica-based bridging pentanoic of silica] zirconium dichloride
Method by (2) among the embodiment 1, (3) step prepares catalyzer, and different is to replace part a and zirconium tetrachloride reaction with part g, and 60 ℃ of the temperature of reaction in the step (2) were reacted 1 hour; Subzero 20 ℃ of step (3) temperature of reaction was reacted 12 hours, catalyzer G:[two (3-nitro-5-chloro salicylic aldehyde) contract 4,4 '-the silica-based bridging pentanoic of silica] zirconium dichloride, productive rate 80%; Catalyst structure is as follows: FI-IR:1640 (C=N), 1257 (Ar-Si), 738 (Zr-N), 508 (Zr-O).
Embodiment 8:[two (5-chloro salicylic aldehyde) contracts 4,4 '-the silica-based bridging pentanoic of silicon nitrogen] preparation of zirconium dichloride
(1) two (5-chloro salicylic aldehyde) contract 4,4 '-preparation of the silica-based bridging pentanoic of silicon nitrogen part
Method by (1) among the embodiment 1 step prepares part, different is with (1) salicylic aldehyde and 4 in step, 4 '-diaminodiphenyl oxide replaces to 5-chloro salicylic aldehyde and 4 respectively, 4 '-the silica-based bridging pentanoic of silicon nitrogen, get part h: two (5-chloro salicylic aldehydes) contract 4,4 '-the silica-based bridging pentanoic of silica, productive rate 80%; FI-IR:3420 (OH), 1616 (C=N), 1263 (Ar-Si);
(2) preparation of [two (5-chloro salicylic aldehydes) contract 4,4 '-the silica-based bridging pentanoic of silicon nitrogen] zirconium dichloride
Method by (2) among the embodiment 1, (3) step prepares catalyzer, and different is to replace part a and zirconium tetrachloride reaction with part g, and subzero 40 ℃ of the temperature of reaction in the step (2) was reacted 4 hours; 100 ℃ of step (3) temperature of reaction were reacted 5 hours, catalyzer H:[two (5-chloro salicylic aldehyde) contract 4,4 '-the silica-based bridging pentanoic of silicon nitrogen] zirconium dichloride, productive rate 80%; Catalyst structure is as follows: FI-IR:1640 (C=N), 1255 (Ar-Si), 738 (Zr-N), 508 (Zr-O).
Embodiment 9:[two (3, the 5-Dibromosalicylaldehyde) contracts 4,4 '-the oxidation dicyclohexyl amine] preparation of zirconium dichloride
(1) two (3, the 5-Dibromosalicylaldehyde) contract 4,4 '-preparation of oxidation dicyclohexyl amine part
Method by (1) among the embodiment 1 step prepares part, different is with (1) salicylic aldehyde and 4 in step, 4 '-diaminodiphenyl oxide replaces to 3 respectively, 5-Dibromosalicylaldehyde and 4,4 '-the oxidation dicyclohexyl amine, get part i: two (3, the 5-Dibromosalicylaldehyde) contract 4,4 '-the oxidation dicyclohexyl amine, productive rate 70%; FI-IR:3420 (OH), 1616 (C=N), 1253 (Ar-O);
(2) preparation of [two (3, the 5-Dibromosalicylaldehyde) contract 4,4 '-oxidation dicyclohexyl amine] zirconium dichloride
Method by (2) among the embodiment 1, (3) step prepares catalyzer, and different is to replace part a and zirconium tetrachloride reaction with part h, gets catalyst I: [two (3, the 5-Dibromosalicylaldehyde) contract 4,4 '-oxidation dicyclohexyl amine] zirconium dichloride, productive rate 67%; Catalyst structure is as follows: FI-IR:1640 (C=N), 1247 (Ar-O), 738 (Zr-N), 508 (Zr-O).
Embodiment 10:[two (3-sec.-propyl salicylic aldehyde) contracts 4,4 '-the isopropylidene dicyclohexyl amine] preparation of zirconium dichloride
(1) two (3-sec.-propyl salicylic aldehyde) contract 4,4 '-preparation of isopropylidene dicyclohexyl amine part
Method by embodiment 1 (1) step prepares part, different is with (1) salicylic aldehyde and 4 in step, 4 '-diaminodiphenyl oxide replace to respectively 3-sec.-propyl salicylic aldehyde and, 4 '-the isopropylidene dicyclohexyl amine, get part j: two (3-sec.-propyl salicylic aldehydes) contract 4,4 '-the isopropylidene dicyclohexyl amine, productive rate 70%; FI-IR:3420 (OH), 1616 (C=N), 1250 (Ar-C);
(2) preparation of [two (3-sec.-propyl salicylic aldehydes) contract 4,4 '-isopropylidene dicyclohexyl amine] zirconium dichloride
Method by (2) among the embodiment 1, (3) step prepares catalyzer, and different is to replace part a and zirconium tetrachloride reaction with part h, get catalyzer J:[two (3-sec.-propyl salicylic aldehyde) to contract 4,4 '-the isopropylidene dicyclohexyl amine] zirconium dichloride, productive rate 67%; Catalyst structure is as follows: FI-IR:1640 (C=N), 1245 (Ar-C), 738 (Zr-N), 508 (Zr-O).
Example 11: vinyl polymerization
Polyreaction is carried out in the 2L polymerization reaction kettle.With the polymeric kettle nitrogen purge, ethene displacement No. 2 times adds the 1L hexane in the still before polymerization, under agitation adds the triethyl aluminum that 1ml concentration is 2mmol/ml and the toluene solution of 5ml catalyst A (4 μ mol) successively; 50 ℃ feed ethylene gas down, keep polymerization pressure 1MPa, and polyreaction 10 minutes stops the input of ethylene gas then, stops to stir.Polymkeric substance with 10% methanol hydrochloride solution washing and filtering after in 60 ℃ of following vacuum-dryings 6 hours, polymkeric substance 2.2g, catalyst activity is 5.5 * 10
6GPE/molCat.h, the viscosity-average molecular weight of resulting polymers is 5.2 * 10
5
Example 12: vinyl polymerization
Polyreaction is carried out in the 2L polymerization reaction kettle.With the polymeric kettle nitrogen purge, ethene displacement No. 2 times adds the 1L hexane in the still before polymerization, under agitation adds the aluminium diethyl monochloride that 10ml concentration is 2mmol/ml and the toluene solution of 5ml catalyst B (40 μ mol) successively.-25 ℃ feed ethylene gas down, keep polymerization pressure 1MPa, and polyreaction 10 minutes stops the input of ethylene gas then, stops to stir.Polymkeric substance with 10% methanol hydrochloride solution washing and filtering after in 60 ℃ of following vacuum-dryings 6 hours, polymkeric substance 8.2g, catalyst activity is 1.2 * 10
6GPE/molCat.h, the viscosity-average molecular weight of resulting polymers is 3.2 * 10
5
Example 13: vinyl polymerization
Polyreaction is carried out in the 2L polymerization reaction kettle.With the polymeric kettle nitrogen purge, ethene displacement No. 2 times adds the 1L hexane in the still before polymerization, under agitation adds triisobutyl aluminium that 0.8ml concentration is 2mmol/ml and the toluene solution of 5ml catalyzer C (16 μ mol) successively.0 ℃ feeds ethylene gas down, keeps polymerization pressure 1MPa, and polyreaction 10 minutes stops the input of ethylene gas then, stops to stir.Polymkeric substance with 10% methanol hydrochloride solution washing and filtering after in 60 ℃ of following vacuum-dryings 6 hours, polymkeric substance 6.4g, catalyst activity is 2.4 * 10
6GPE/molCat.h, the viscosity-average molecular weight of resulting polymers is 4.2 * 10
5
Example 14: vinyl polymerization
Polyreaction is carried out in the 2L polymerization reaction kettle.With the polymeric kettle nitrogen purge, ethene displacement No. 2 times adds the 1L hexane in the still before polymerization, under agitation adds tri-n-octylaluminium that 16ml concentration is 2mmol/ml and the toluene solution of 5ml catalyzer D (16 μ mol) successively.75 ℃ feed ethylene gas down, keep polymerization pressure 1MPa, and polyreaction 10 minutes stops the input of ethylene gas then, stops to stir.Polymkeric substance with 10% methanol hydrochloride solution washing and filtering after in 60 ℃ of following vacuum-dryings 6 hours, polymkeric substance 18.2g, catalyst activity is 6.4 * 10
6GPE/molCat.h, the viscosity-average molecular weight of resulting polymers is 5.8 * 10
5
Example 15: vinyl polymerization
Polyreaction is carried out in the 2L polymerization reaction kettle.With the polymeric kettle nitrogen purge, ethene displacement No. 2 times adds the 1L hexane in the still before polymerization, under agitation adds 8ml concentration successively and be the methylaluminoxane of triisobutyl aluminium modification of 2mmol/ml and the toluene solution of 5ml catalyzer E (16 μ mol).100 ℃ feed ethylene gas down, keep polymerization pressure 1MPa, and polyreaction 10 minutes stops the input of ethylene gas then, stops to stir.Polymkeric substance with 10% methanol hydrochloride solution washing and filtering after in 60 ℃ of following vacuum-dryings 6 hours, polymkeric substance 6.0g, catalyst activity is 2.3 * 10
6GPE/molCat.h, the viscosity-average molecular weight of resulting polymers is 3.9 * 10
5
Example 16: vinyl polymerization
Polyreaction is carried out in the 2L polymerization reaction kettle.With the polymeric kettle nitrogen purge, ethene displacement No. 2 times adds the 1L hexane in the still before polymerization, under agitation adds methylaluminoxane that 8ml concentration is 2mmol/ml and the toluene solution of 5ml catalyzer F (16 μ mol) successively.70 ℃ feed ethylene gas down, keep polymerization pressure 0.1MPa, and polyreaction 20 minutes stops the input of ethylene gas then, stops to stir.Polymkeric substance with 10% methanol hydrochloride solution washing and filtering after in 60 ℃ of following vacuum-dryings 6 hours, polymkeric substance 15.5g, catalyst activity is 5.8 * 10
6GPE/molCat.h, the viscosity-average molecular weight of resulting polymers is 5.1 * 10
5
Example 17: vinyl polymerization
Polyreaction is carried out in the 2L polymerization reaction kettle.With the polymeric kettle nitrogen purge, ethene displacement No. 2 times adds the 1L hexane in the still before polymerization, under agitation adds MAO that 4ml concentration is 2mmol/ml and the toluene solution of 5ml catalyzer G (5 μ mol) successively.35 ℃ feed ethylene gas down, keep polymerization pressure 0.4MPa, and polyreaction 10 minutes stops the input of ethylene gas then, stops to stir.Polymkeric substance with 10% methanol hydrochloride solution washing and filtering after in 60 ℃ of following vacuum-dryings 6 hours, polymkeric substance 9.2g, catalyst activity is 1.1 * 10
7GPE/molCat.h, the viscosity-average molecular weight of resulting polymers is 5.6 * 10
5
Example 18: vinyl polymerization
Polyreaction is carried out in the 2L polymerization reaction kettle.With the polymeric kettle nitrogen purge, ethene displacement No. 2 times adds the 1L hexane in the still before polymerization, under agitation adds MAO that 4ml concentration is 2mmol/ml and the toluene solution of 5ml catalyzer H (5 μ mol) successively.35 ℃ feed ethylene gas down, keep polymerization pressure 1.2MPa, and polyreaction 10 minutes stops the input of ethylene gas then, stops to stir.Polymkeric substance with 10% methanol hydrochloride solution washing and filtering after in 60 ℃ of following vacuum-dryings 6 hours, polymkeric substance 7.2g, catalyst activity is 8.7 * 10
6GPE/molCat.h, the viscosity-average molecular weight of resulting polymers is 4.2 * 10
5
Example 19: vinyl polymerization
Polyreaction is carried out in the 2L polymerization reaction kettle.With the polymeric kettle nitrogen purge, ethene displacement No. 2 times adds the 1L hexane in the still before polymerization, under agitation adds the MAO that 4ml concentration is 2mmol/ml and the toluene solution of 5ml catalyst I (5 μ mol) successively.35 ℃ feed ethylene gas down, keep polymerization pressure 1.5MPa, and polyreaction 10 minutes stops the input of ethylene gas then, stops to stir.Polymkeric substance with 10% methanol hydrochloride solution washing and filtering after in 60 ℃ of following vacuum-dryings 6 hours, polymkeric substance 17.5g, catalyst activity is 2.1 * 10
7GPE/molCat.h, the viscosity-average molecular weight of resulting polymers is 7.2 * 10
5
Example 20: vinyl polymerization
In the 2L polymerization reaction kettle, carry out.With the polymeric kettle nitrogen purge, ethene displacement No. 2 times adds the 1L hexane in the still before polymerization, under agitation adds the MAO that 4ml concentration is 2mmol/ml and the toluene solution of 5ml catalyst I (5 μ mol) successively.35 ℃ feed ethylene gas down, keep polymerization pressure 0.1MPa, and polyreaction 40 minutes stops the input of ethylene gas then, stops to stir.Polymkeric substance with 10% methanol hydrochloride solution washing and filtering after in 60 ℃ of following vacuum-dryings 6 hours, polymkeric substance 15g, catalyst activity is 1.8 * 10
7GPE/molCat.h, the viscosity-average molecular weight of resulting polymers is 5.9 * 10
5
Claims (10)
1. tooth IVB group 4 transition metal catalyzer is characterized in that structure is as follows:
R in the formula
1Be the substituting group on the phenyl ring, the replacement radix on each phenyl ring is 1～4, R
1Be hydrogen, C
1～C
6Alkyl, sec.-propyl, tertiary butyl, phenyl, cumyl, methoxyl group, nitroxyl or halogen; R
2Be hydrogen or C
1～C
3Alkyl; M is an IVB family metal; X is a halogen; Y is a bridged group; Z is
Or have a substituent phenyl ring.
2. a kind of four tooth IVB group 4 transition metal catalyzer according to claim 1 is characterized in that described substituent R
1Be positioned at 3～6 of phenyl ring.
3. a kind of four tooth IVB group 4 transition metal catalyzer according to claim 1 is characterized in that described halogen is a chlorine or bromine; M is titanium or zirconium.
4. a kind of four tooth IVB group 4 transition metal catalyzer according to claim 1 is characterized in that described Z is with substituent phenyl ring, and structure is as follows:
R wherein
3Be hydrogen, C
1～C
6Alkyl, sec.-propyl or tertiary butyl; R
4Be hydrogen, C
1～C
6Alkyl.
5. a kind of four tooth IVB group 4 transition metal catalyzer according to claim 1, it is characterized in that described Y be-O-,-S-,-MeN-,-CH
2-,-MeCH-,-Me
2C-,-CH
2-Me
2C-CH
2-,-(Ph)
2C-,-(Me)
2Si-,-(Ph)
2Si-,-(Me)
2Ge-,-(Me)
2Sn-,-(Me)
2Si-O-Si (Me)
2-,-(Me)
2Si-MeN-Si (Me)
2-or-(Me)
2Si-
nBuN-Si (Me)
2-.
6. tooth IVB group 4 transition metal Preparation of catalysts method, its feature comprises the steps: in it
(1) under the anhydrous and oxygen-free condition, in alcoholic solvent, be catalyzer with the organic acid, with substituted salicylic aldehydes and bridging diamine compounds, carry out the Schiff's base condensation reaction by 2: 1 mol ratio down at 0～100 ℃, remove and desolvate, the gained solid drying is promptly got ligand compound with four toothings;
(2) under the anhydrous and oxygen-free condition, in tetrahydrofuran solvent, the above-mentioned ligand compound that makes and basic metal, alkali metal compound or alkaline earth metal compound are reacted down at-40～60 ℃ by 1: 2 mol ratio, make basic metal or alkaline earth salt;
(3) under the anhydrous and oxygen-free condition, in tetrahydrofuran solvent, will make basic metal or alkaline earth salt and MX
4Transition metal halide reacts down at-40～100 ℃ by 1: 1 mol ratio, removes tetrahydrofuran solvent, and resistates organic substance extraction, extract concentrate the back chromatography and get four tooth transition-metal catalysts.
7. a kind of four tooth IVB group 4 transition metal Preparation of catalysts methods according to claim 6 is characterized in that described alcoholic solvent of (1) step is methyl alcohol or ethanol, and organic acid is formic acid or acetate; (2) go on foot described basic metal for receiving or potassium, alkali metal compound is that butyllithium or hydrogenation are received, and alkaline earth metal compound is methylmagnesium-chloride or ethylmagnesium chloride; (3) go on foot described MX
4Transition metal halide is titanium tetrachloride or zirconium tetrachloride, and the organic solvent that is used for extracted residues is methylene dichloride or toluene, and concentration method adopts concentrating under reduced pressure or cryogenic freezing to concentrate, and the chromatography solvent is normal hexane or sherwood oil.
8. a kind of four tooth IVB group 4 transition metal Preparation of catalysts methods according to claim 6 is characterized in that described bridging diamine compounds structure is:
9. the application of a tooth IVB group 4 transition metal catalyzer in olefinic polymerization, it is characterized in that with four tooth IVB group 4 transition metal catalyzer be Primary Catalysts, with aluminum alkyls or aikyiaiurnirsoxan beta is promotor, in hexane, methylene dichloride or toluene solvant, make alkene under-25～100 ℃, 0.1～2MPa condition, carry out polyreaction; Primary Catalysts concentration is 0.1～1000 μ mol/L during reaction, in the promotor in Al and the Primary Catalysts mol ratio of metal be 10～3000: 1.
10. a kind of four application of tooth IVB group 4 transition metal catalyzer in olefinic polymerization according to claim 9 is characterized in that described aluminum alkyls is triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium or tri-n-octylaluminium; Aikyiaiurnirsoxan beta is a methylaluminoxane or through the methylaluminoxane of triisobutyl aluminium modification.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102382256A (en) * | 2011-08-23 | 2012-03-21 | 浙江大学 | Catalyst system and preparation method for norbornene and isoprene copolymer |
| CN102516424A (en) * | 2011-12-09 | 2012-06-27 | 沈阳工业大学 | Tetradentate titanium complex, composite carrier loaded tetradentate titanium catalyst, its preparation method and its application |
| CN102516291A (en) * | 2011-12-09 | 2012-06-27 | 沈阳工业大学 | Schiff base transition metal complex containing alkoxy groups, and preparation method and application thereof |
| JP2015182992A (en) * | 2014-03-26 | 2015-10-22 | 三井化学株式会社 | Transition metal compound, olefin polymerization catalyst, and olefin-based polymer production method |
| CN113321674A (en) * | 2021-06-28 | 2021-08-31 | 山东京博石油化工有限公司 | [ NOON ] quadridentate ligand fourth subgroup metal complex and application thereof |
| CN117430525A (en) * | 2023-03-01 | 2024-01-23 | 中化学科学技术研究有限公司 | Schiff base ligand and preparation method and application thereof |
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