CN1302017C - Process for preparing olefin polymerizing catalyst of [R-N,P] 1-type double tooth ligand and post transition metal coordination - Google Patents
Process for preparing olefin polymerizing catalyst of [R-N,P] 1-type double tooth ligand and post transition metal coordination Download PDFInfo
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- CN1302017C CN1302017C CNB2004100893169A CN200410089316A CN1302017C CN 1302017 C CN1302017 C CN 1302017C CN B2004100893169 A CNB2004100893169 A CN B2004100893169A CN 200410089316 A CN200410089316 A CN 200410089316A CN 1302017 C CN1302017 C CN 1302017C
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Abstract
The present invention relates to an 'after cyclopentadiene' [RminusN, P]<1 minus>type double-tooth ligand and post transition metal coordination olefin polymerization catalyst and a synthetic process thereof, and the application of the catalyst on catalyzing norbornene polyreaction. The catalyst has an expression of [LminusMR1R2], wherein L represents a double-tooth ligand contains N and P atoms which can be coordinated with metal; R1 represents Ph or CH3, R2 represents PPh3 or CH3 and CN, and M represents one of metal Ni or Pd. The catalyst and methylaluminoxane or modified methylaluminoxane are matched in the catalyzing norbornene polyreaction. The catalyst has high catalytic activity. The catalyst has the advantages of simple preparation and high stability, and a polynorbornene product with high molecular weight, high glass transition temperature and peculiar property can be obtained.
Description
Technical field
The invention belongs to [R-N, P]
1-The preparation method of the olefin polymerization catalysis of type bitooth ligand and post transition metal coordination and the application in the preparation of polynorbornene.
Technical background
The R and D of polyolefine synthesis technique are one of popular research topics of polymer chemistry and plastics industry.Polyolefine is the mainstay industry of modern macromolecular material industry, and olefin polymerization catalysis then is the core of polyolefine industry.Because the organo-metallic olefin polymerization catalysis not only can efficient catalytic olefinic polymerization under the condition of gentleness, and microtexture that can the cutting polymkeric substance, so can on molecular level, design the new function polyolefine material and improve existing polymer properties, so the research in this field is one of contemporary chemical forward position and focus always.Since nineteen fifty-three, olefin polymerization catalysis came out, Ziegler-Natta catalyst system, metallocene catalysis system and three important milestones of rear transition metal catalyst system had appearred in short five ten years.
Norbornylene has three kinds of polymerization methodses: ring-opening metathesis polymerization, positively charged ion or radical polymerization and add-on type polymerization.Before the mid-80, to norbornene polymerization research more be ring-opening metathesis polymerization.Because this type of polymerization has kept two keys, thereby can be by the crosslinked superpolymer that obtains having higher elasticity.Use RuCl in the business-like polymerization technique
3/ HCl catalyst system.And the research of relevant positively charged ion or radical polymerization is less, and products therefrom is the norbornylene oligopolymer of 2,7 connections of low relative molecular mass.1963, Sartori etc. at first reported the addition polymerization of norbornylene, but had shortcomings such as catalytic activity is not high, molecular weight is low.Kaminsky etc. adopt this catalyst system to carry out the norbornylene addition polymerization and have obtained very big progress after finding metallocene/methylaluminoxane (MAO) efficient catalytic system, gained polynorbornene Heat stability is good, but product is insoluble to organic solvent, processing difficulties.Late transition metal catalyst also constantly is applied to the addition polymerization of norbornylene in recent years.Deming in 1993 and Novak have reported that the complex compound of first nickel is used for the add-on type polymerization research of norbornylene.Because add-on type norbornylene homopolymer has a series of uniquenesses and interesting physical and chemical performance, for example high chemical impedance, solvability preferably, good ultraviolet impedance, low-k, high glass transition temperature, good translucidus, high specific refractory power and low-birefringence etc. are arranged in organic solvent, thereby the polymerization studies of this respect is seen in bibliographical information constantly in recent years.
Traditional catalyzer has been finished industrialization at present, and metallocene catalysis system has different separately characteristics with " luxuriant back " the transition metal-catalyzed system that is now just becoming the research focus.Research to " luxuriant back " transistion metal compound since nineteen ninety-five has obtained remarkable progress, has found many new catalyzer.The typical catalyst of nickel system is that active centre nickel (II) forms title complex with organic ligand, and it is the diimine neutral ligand of N, N that part research at present mainly concentrates on the ligating atom, and ligating atom is the anion ligand of P, O and N, O etc.In recent years, P, N part have caused increasing concern, and this mainly is owing to itself and the electronics of metal center coordinate diversity and donor atom and the reason that spatial character is easy to regulate.Braunstein research group has synthesized the complex compound of the nickel of a series of P of containing, N sequestration ligand, and comparatively systematic research the ethylene oligomerization behavior of complex compound.
Typical nickel is P, the N structure that characterizes sequestration ligand as shown in following:
Summary of the invention
The purpose of this invention is to provide a kind of [R-N, P]
1-Olefin polymerization catalysis of type bitooth ligand and post transition metal coordination and preparation method thereof.
Olefin polymerization catalysis provided by the invention is with THF, Et
2O, toluene or benzene are solvent, are starting raw material by Ortho-Chloro aniline, triphenyl phosphorus and anhydrous chlorides of rase nickel, make ligand L through reaction
1-2-diphenylphosphine aniline; Ligand L
1Through equimolar amount
nBuLi pulls out behind the hydrogen and CH again
3The I effect has made ligand L
2-2-diphenylphosphine n-formyl sarcolysine base aniline.Ligand L
2With equimolar amount
nBuLi reaction generates the lithium salts of part, then with the trans-[M (R of equimolar amount
2)
2(R
1) Cl] reaction, through extracting, filter, wash, vacuumize drying.Obtain corresponding catalyzer, productive rate is 68%--77%, and entire reaction course can be expressed as follows:
Such catalyzer is the homogeneous phase single site catalysts, has advantages of high catalytic activity under the condition of gentleness, by changing the substituted radical on the part, can obtain the polynorbornene of different molecular weight with different active catalytic.
The expression formula of the catalyzer of the present invention's preparation is [L-MR
1R
2], wherein, L represent a kind of contain can with the N of metal-complexing, the bitooth ligand of P atom, R
1Expression Ph or CH
3, R
2Expression PPh
3Or CH
3CN, M represent a kind of of metal Ni or Pd, and concrete structure is shown below:
Wherein M is a kind of of central metal Ni, Pd, and R is H or CH
3
In the above-mentioned catalyzer, get R=H, R
1=Ph, R
2=PPh
3
This class [R-N, P]
1-The olefin polymerization catalysis of type part and post transition metal coordination yet there are no document or patent report so far.
[R-NP]
1-The olefin polymerization catalysis preparation process of type bitooth ligand and post transition metal coordination is as follows:
(1) preparation of 2-diphenylphosphine aniline:
Its structural formula is:
Get the 2-chloroaniline of 0.05-0.5mol, the PPh of 0.05-0.5mol
3(triphenyl phosphorus) adds the Powdered anhydrous chlorides of rase nickel of 0.025-0.25mol then in the 50-500mL round-bottomed flask.Stir down mixture heating up to 200 ~ 220 ℃, reacted 3-5 hour, obtain the melts of black and blue color, melts is cooled to 180 ~ 160 ℃, join in the sour acidifying 55-65 of 30-300mL ℃ the hot water; With other 20-200mL ebullient acidified water extraction melts, decorporate fully until the blueness of melts, merge acidified water.Be cooled to room temperature.(1 * 15-150mL, 2 * 10-100mL) washings are used CH to remove unreacted starting raw material to water then with ether
2Cl
2(3 * 15-150mL) extractions, combining extraction liquid is also used anhydrous Na
2SO
4Drying, revaporization is to yellow oil (about 15-150mL).The THF that adds about 25-250mL under the violent stirring has just begun to form until white crystals, and the mixture of gained was placed in about about 4-10 ℃ 5-10 hour; Filter white crystal, respectively with the washing of THF and ether, dry more than 12 hours in (about 15torr) under 100-130 ℃ then again, removing residual solvent, the about 11.1-111g of product (57%) that must white powder, m.p.:293 ~ 295 ℃.
Under nitrogen atmosphere, in three mouthfuls of round-bottomed flasks of 150-500mL exsiccant, add the THF of about 50-150mL, 0.039-0.117mol naphthalene and 0.036-0.108mol sodium silk are stirred to sodium then and dissolve fully, need 1 hour approximately.The green ochre look solution that obtains is cooled to cryostat and almost completely becomes solid; Add the front then and obtain rolling over toner powder product 0.0164-0.0492mol.Mixture stirred 50-70 minute after rising to room temperature naturally; Dropwise add about 0.2-0.6g acetate then, to eliminate remaining green.The mixture of the orange that obtains is handled with the ammonium chloride solution of 10-30mL20%, and the water that adds capacity again is to dissolve the solid of any remnants.Two be separated after, (1 * 10-30mL) extraction is used anhydrous Na after organic phase merges to water with ether
2SO
4Drying is filtered, evaporation.Resistates places the ethanol of 50mL ebullient 90%, and with Nickelous nitrate hexahydrate solution-treated (2.6-7.8g, 0.009-0.027mol be dissolved in 10-30mL ebullient 90% ethanol), the gained brown solution is handled to guarantee that the amino proton that takes off no longer takes place with the trifluoroacetic acid of 0.2-0.6mL.5 ℃ stored more than 12 hours, filter metal composite and crystalline naphthalene; Wash to remove naphthalene with ether again with ethanol earlier then, get 5.54-16.62g (89%) yellow crystals [Ni (L
1)
2] (NO
3)
2H
2O is the complex compound of nickel.
The complex compound of nickel is suspended in the mixture of benzene (30-90mL) and water (30-90mL), and adds several concentrated hydrochloric acids, mixture is back to dissolution of crystals.Two be separated after, water merges organic layer with benzene (5-15mL) extraction, with salt solution (10-30mL) washing, uses anhydrous Na
2SO
4Post (the Al of 2.5 * 10cm is crossed in dry back
2O
3Post), use the benzene wash-out.The colourless solution that obtains is evaporated to oily, places 18-54mL ebullient 90% ethanol then.The white crystal 3.56-10.68g that cools off loosely is 2-diphenylphosphine aniline.M.p.:82 ~ 83 ℃ (88%) from the complex compound calculating of nickel.
(2) preparation of 2-diphenylphosphine n-formyl sarcolysine base aniline part:
Its structural formula is:
Ligand L with 2.0-4.0mmol
1Be dissolved among the anhydrous THF that 20-40mL handled, drip down at subzero 78 ℃
nBuLi2.0-4.0mmol stirred 2-3 hour.The CH that in low temperature downhill reaction liquid, dropwise adds 0.125-0.25mL (2.0-4.0mmol)
3I reacts and is warming up to room temperature after 3-5 hour, leaves standstill more than 12 hours, and reaction is ended with the water of the 3-6mL degassing, and with extracted with diethyl ether (3 * 3-6mL), separation organic layer, and use anhydrous MgSO
4Drying is filtered, and last solvent removed in vacuo gets product.
(3) with [R-N, P]
1-The preparation of type bitooth ligand coordinate late transition metal catalyst:
Its structural formula is:
Carry out under the protection of Preparation of catalysts and high pure nitrogen anhydrous in anaerobic.Ligand L with 1-20mmol
2Be dissolved among the anhydrous THF of 20-400 milliliter, drip below 78 ℃ subzero
nBuLi 1-20mmol stirred 2-3 hour, the mixed solution that reacts is added drop-wise at leisure contains 1-20mmol trans-[M (R
2)
2(R
1) Cl] and toluene solution in.At room temperature stirred 12-16 hour, centrifugal precipitation of removing lithium salts, the vacuum concentration solvent adds a large amount of normal hexanes so that precipitation is separated out.After vacuum filtration removed and desolvates, with normal hexane washing 3-5 time, vacuum-drying promptly obtained described catalyzer to precipitation, productive rate 68-77% again.
Use the step of catalyst norbornylene polyaddition reaction provided by the invention as follows:
The norbornylene addition polymerization is carried out under the anhydrous and oxygen-free condition.Nitrogen atmosphere adds the chlorobenzene solution (content is 0.2-2 μ mol) of the aforementioned catalyzer of 2-20mL down successively in polymerization bottle with syringe, stir and add the chlorobenzene solution (content is 20-200mmol) of 3-30mL norbornylene and the chlorobenzene of 3-30mL down, kept 5-10 minute, add 0.066-1.32mL promotor MAO or MMAO (wherein, Al/Ni=500-10000: toluene solution 1), initiated polymerization, the cumulative volume of reaction system generally remains on 10-100mL (adjusting of different volumes useable solvents chlorobenzene), reacted 8-15 minute, and said mixture was poured in the acidifying ethanolic soln into (ethanol: HCl wherein
Conc=95: 5).With polymer filtration, and with washing with alcohol 2-3 time, 70-90 ℃ following vacuum-drying 45-55 hour.The active amt level is 10
6~ 10
7G PNB/ (mol Nih), the polynorbornene molecular weight order of magnitude is 10
6G/mol.
Embodiment
The invention is further illustrated by the following examples.
The preparation of embodiment 1:2-diphenylphosphine aniline:
Get 6.4g (0.05mol, 5.30mL) PPh of 2-chloroaniline, 13.1g (0.05mol)
3In the 50mL round-bottomed flask, add the Powdered anhydrous chlorides of rase nickel of 3.25g (0.025mol) then.Mixture is heated to 200 ℃ under stirring, and maintains the temperature at 200 ~ 220 ℃ of reactions 4 hours.The melts of black and blue color is cooled to and is poured into after 180 ~ 160 ℃ in the hot water that about 30mL used 60 ℃ of sour acidifying; With other 20mL ebullient acidified water extraction melts, decorporate fully until the blueness of melts, merge acidified water.After the cooling, (1 * 15mL, 2 * 10mL) washings are used CH to remove unreacted starting raw material to water then with ether
2Cl
2(3 * 15mL) extractions, combining extraction liquid is also used anhydrous Na
2SO
4Drying, revaporization is to yellow oil (about 15mL).The THF that adds about 25mL under the violent stirring has just begun to form until white crystals, the mixture of gained is placed several hrs in about about 5 ℃, filter afterwards white crystal, again respectively with THF and ether washing, then under 120 ℃ (about 15torr) dried overnight to remove residual solvent, the about 11.1g of product (57%) of white powder, m.p.:293 ~ 295 ℃.
In three mouthfuls of round-bottomed flasks of 150mL exsiccant, add the THF of about 50mL, 5.1g (0.039mol) naphthalene, 0.83g (0.036mol) sodium silk, and in nitrogen atmosphere, be stirred to sodium and dissolve fully, need are 1 hour approximately.The green ochre look solution that obtains is cooled to cryostat and almost completely becomes solid; Add the product 6.4g (0.0164mol) that obtains previously then.Mixture stirred 1 hour after rising to room temperature naturally; Dropwise add about 0.2g (0.003mol) acetate then, to eliminate remaining green.The mixture of orange is handled with the ammonium chloride solution of 10mL20%, and the water that adds capacity again is to dissolve the solid of any remnants.Two be separated after, (1 * 10mL) extraction is used anhydrous Na after organic phase merges to water with ether
2SO
4Drying is filtered, evaporation.Resistates places the ethanol of 50mL ebullient 90%, and with Nickelous nitrate hexahydrate solution-treated (2.6g, 0.009mol are dissolved in 10mL ebullient 90% ethanol), the gained brown solution is handled to guarantee that the amino proton that takes off no longer takes place with the trifluoroacetic acid of 0.2mL.5 ℃ of store overnight, filter metal composite and crystalline naphthalene; Wash to remove naphthalene with ether again with ethanol earlier then, get 5.54g (89%) yellow crystals [Ni (L
1)
2] (NO
3)
2H
2O.
The complex compound of nickel is suspended in the mixture of benzene (30mL) and water (30mL), and adds several concentrated hydrochloric acids, and mixture backflow several hrs is to dissolution of crystals.Two be separated after, water merges organic layer with benzene (5mL) extraction, with salt solution (10mL) washing, uses anhydrous Na
2SO
4Post (the Al of 2.5 * 10cm is crossed in dry back
2O
3Post), use the benzene wash-out.The colourless solution that obtains is evaporated to oily, then as in 18mL ebullient 90% ethanol.The white crystal 3.56g that cools off loosely, m.p.:82 ~ 83 ℃ (88%) from the complex compound calculating of nickel.
The preparation of embodiment 2:2-diphenylphosphine n-formyl sarcolysine base aniline part:
With the ligand L that makes among 0.555g (2.0mmol) embodiment 1
1Be dissolved among the anhydrous THF of processing of 20mL, drip down at subzero 78 ℃
nBuLi 2.0mmol stirred 2-3 hour.The CH that in low temperature downhill reaction liquid, dropwise adds 0.125mL (2.0mmol)
3I is warming up to room temperature behind the reaction 4h, spends the night.Reaction is ended with the water of the 3mL degassing, and with extracted with diethyl ether (3 * 3mL), separation organic layer, and use anhydrous MgSO
4Drying is filtered, and last solvent removed in vacuo gets product.
Embodiment 3: with [R-N, P]
1-The preparation of type bitooth ligand coordinate late transition metal catalyst:
Carry out under the protection of Preparation of catalysts and high pure nitrogen anhydrous in anaerobic.With the ligand L that makes among 0.277g (1.0mmol) embodiment 1
1Be dissolved among the anhydrous THF that 20mL handled, drip down for subzero 78 ℃ at low temperature
n(2.3M 1mmol), stirs after 2-3 hour BuLi 0.48mL, the mixed solution that reacts is added drop-wise at leisure contains 0.668g (0.96mmol) trans-[Ni (PPh
3)
2(Ph) Cl] toluene solution in.After at room temperature stirring 12-16 hour, centrifugal precipitation of removing lithium salts, the vacuum concentration solvent adds a large amount of normal hexanes so that precipitation is separated out.After vacuum filtration removed and desolvates, precipitation with normal hexane washing 3-5 time, was drained vacuum-drying again, obtains corresponding catalyzer 0.499g, productive rate 77%.
Embodiment 4: with [R-NP]
1-The preparation of type bitooth ligand coordinate late transition metal catalyst:
Get the ligand L that makes among 0.291g (1.0mmol) embodiment 2
2Be dissolved among the anhydrous THF that 20mL handled, drip down for subzero 78 ℃ at low temperature
n(2.3M 1mmol), stirs after 2-3 hour BuLi 0.48mL, the mixed solution that reacts is added drop-wise at leisure contains 0.668g (0.96mmol) trans-[Ni (PPh
3)
2(Ph) Cl] toluene solution in.After at room temperature stirring 12-16 hour, centrifugal precipitation of removing lithium salts, the vacuum concentration solvent adds a large amount of normal hexanes so that precipitation is separated out.After vacuum filtration removed and desolvates, precipitation with normal hexane washing 3-5 time, was drained vacuum-drying again, obtains corresponding catalyzer 0.449g, productive rate 68%.
Embodiment 5: catalysis norbornylene polyaddition reaction:
Nitrogen atmosphere adds down the chlorobenzene solution (0.2 μ molNi) of the catalyzer that 2.0mL embodiment 3 makes successively in the Schlenk bottle with syringe.Add 3.0mL norbornylene chlorobenzene solution (20.0mmol under the violent stirring, 1.88g) and the 3mL chlorobenzene, under 30 ℃, keep 5-10min, add the toluene solution of 0.132mL (1000: 1 Al/Ni) promotor MAO, initiated polymerization, the cumulative volume of reaction system generally remain on 10mL (adjusting of different volumes useable solvents chlorobenzene), behind the reaction 10min, pour mixture in the acidifying ethanolic soln (ethanol/HCl
Conc=95: 5) termination reaction.With polymer filtration, and with washing with alcohol 3 times, 80 ℃ of following vacuum-drying 48 hours, polynorbornene 1.05g, activity is 3.14 * 10
7G PNB/ (molNih), molecular weight are 2.71 * 10
6G/mol.
Embodiment 6: catalysis norbornylene polyaddition reaction:
The norbornene polymerization operation is with embodiment 5, and the catalyzer 0.2 μ mol (pressing Al/Ni=2000) of methylaluminoxane (MAO) 0.265mL, embodiment 3 preparations gets polynorbornene 1.13g, and activity is 3.39 * 10
7GPNB/ (mol Nih), the molecular weight of polynorbornene is 2.61 * 10
6G/mol.
Embodiment 7: catalysis norbornylene polyaddition reaction:
The norbornene polymerization operation is with embodiment 5, and the catalyzer 0.2 μ mol (pressing Al/Ni=3000) of methylaluminoxane (MAO) 0.397mL, embodiment 3 preparations gets polynorbornene 1.30g, and activity is 3.90 * 10
7GPNB/ (mol Nih), molecular weight is 2.57 * 10
6G/mol.
Embodiment 8: catalysis norbornylene polyaddition reaction:
The norbornene polymerization operation is with embodiment 5, and the catalyzer 0.2 μ mol (pressing Al/Ni=4000) of methylaluminoxane (MAO) 0.530mL, embodiment 3 preparations gets polynorbornene 1.12g, and activity is 3.36 * 10
7G PNB/ (mol Nih), the molecular weight of polynorbornene is 2.06 * 10
6G/mol.
Embodiment 9: catalysis norbornylene polyaddition reaction:
The norbornene polymerization operation is with embodiment 5, and the catalyzer 0.2 μ mol (pressing Al/Ni=5000) of methylaluminoxane (MAO) 0.662mL, embodiment 3 preparations gets polynorbornene 1.06g, and activity is 3.18 * 10
7G PNB/ (mol Nih), the molecular weight of polynorbornene is 2.88 * 10
6G/mol.
Embodiment 10: catalysis norbornylene polyaddition reaction:
The norbornene polymerization operation is with embodiment 5, and the catalyzer 0.2 μ mol (pressing Al/Ni=10000) of methylaluminoxane (MAO) 1.32mL, embodiment 3 preparations gets polynorbornene 1.03g, and activity is 3.09 * 10
7GPNB/ (mol Nih), the molecular weight of polynorbornene is 3.07 * 10
6G/mol.
Embodiment 11: catalysis norbornylene polyaddition reaction:
Norbornene polymerization operation is with embodiment 5, and the catalyzer 0.2 μ mol (pressing Al/Ni=500) of methylaluminoxane (MAO) 0.066mL, embodiment 3 preparations gets only the polynorbornene of trace.
Embodiment 12: catalysis norbornylene polyaddition reaction:
Converging operation is with embodiment 7, and polymerization temperature is 0 ℃, gets polynorbornene 0.309g, and activity is 9.27 * 10
6G PNB/ (mol Nih), molecular weight is 2.80 * 10
6G/mol.
Embodiment 13: catalysis norbornylene polyaddition reaction:
Converging operation is with embodiment 7, and polymerization temperature is 60 ℃, gets polynorbornene 1.08g, and activity is 3.24 * 10
7G PNB/ (mol Nih), molecular weight is 1.81 * 10
6G/mol.
Embodiment 14: catalysis norbornylene polyaddition reaction:
Converging operation is with embodiment 7, and polymerization temperature is 90 ℃, gets polynorbornene 0.799g, and activity is 2.40 * 10
7G PNB/ (mol Nih), molecular weight is 1.37 * 10
6G/mol.
Embodiment 15: catalysis norbornylene polyaddition reaction:
Nitrogen atmosphere adds down the chlorobenzene solution (0.2 μ molNi) of the catalyzer that 2.0mL embodiment 4 makes successively in the Schlenk bottle with syringe.Add 3.0mL norbornylene chlorobenzene solution (20.0mmol under the violent stirring, 1.88g) and the 3mL chlorobenzene, under 30 ℃, keep 5-10min, add the toluene solution of 0.397mL (3000: 1 Al/Ni) promotor MAO, initiated polymerization, the cumulative volume of reaction system generally remain on 10mL (adjusting of different volumes useable solvents chlorobenzene), behind the reaction 10min, pour mixture in the acidifying ethanolic soln (ethanol/HCl
Conc=95: 5) termination reaction.With polymer filtration, and with washing with alcohol 3 times, 80 ℃ of following vacuum-drying 48 hours, polynorbornene 0.942g, activity is 2.83 * 10
7G PNB/ (mol Nih), molecular weight is 2.46 * 10
6G/mol.
Embodiment 16: catalysis norbornylene polyaddition reaction:
The norbornene polymerization operation is with embodiment 15, and the catalyzer 0.2 μ mol (pressing Al/Ni=4000) of methylaluminoxane (MAO) 0.530mL, embodiment 3 preparations gets polynorbornene 0.808g, and activity is 2.24 * 10
7G PNB/ (mol Nih), the molecular weight of polynorbornene is 2.28 * 10
6G/mol.
Claims (3)
1, a kind of [R-N, P]
1-The olefin polymerization catalysis of type bitooth ligand and post transition metal coordination is characterized in that its expression formula is [L-MR
1R
2], wherein, L represent to contain can with the N of metal-complexing, the bitooth ligand of P atom, R
1Expression Ph or CH
3, R
2Expression PPh
3Or CH
3CN, M represent a kind of of metal Ni or Pd, and concrete structure is shown below:
Wherein M is a kind of of central metal Ni, Pd, and R is H or CH
3
2, a kind of [R-N, P] as claimed in claim 1
1-The preparation method of the olefin polymerization catalysis of type bitooth ligand and post transition metal coordination is characterized in that step is as follows:
With THF, Et
2O, toluene or benzene are solvent, are starting raw material with Ortho-Chloro aniline, triphenyl phosphorus and anhydrous chlorides of rase nickel, make ligand L through reaction
1-2-diphenylphosphine aniline; Ligand L
1Through equimolar amount
nBuLi pulls out hydrogen, again with CH
3The I effect makes ligand L
2-2-diphenylphosphine n-formyl sarcolysine base aniline; Ligand L
2With equimolar amount
nBuLi reaction generates the lithium salts of part, the trans-[M (R of last and equimolar amount
2)
2(R
1) Cl] reaction, through extraction, filtration, washing, vacuumize drying and obtain corresponding catalyzer.
3, a kind of [R-N, P] as claimed in claim 1
1-The using method of the olefin polymerization catalysis of type bitooth ligand and post transition metal coordination, it is characterized in that, be used for the norbornylene addition polymerization, under the anhydrous and oxygen-free condition, carry out, concrete steps are as follows: add the chlorobenzene solution that 2-20mL contains the described catalyzer of 0.2-2 μ mol under the nitrogen atmosphere in polymerization bottle successively, add the chlorobenzene solution of 3-30mL 20-200mmol norbornylene and the chlorobenzene of 3-30mL under stirring, kept 5-10 minute, add 0.066-1.32mL Al/Ni=500-10000: 1 catalyzer MAO or the toluene solution of MMAO, initiated polymerization, the cumulative volume of reaction system remains on 10-100mL, react after 8-15 minute, mixture is poured in the acidifying ethanolic soln; With polymer filtration, and with washing with alcohol 2-3 time, 70-90 ℃ following vacuum-drying 45-55 hour.
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| US6410664B1 (en) * | 1997-03-24 | 2002-06-25 | Cryovac, Inc. | Catalyst compositions and processes for olefin polymers and copolymers |
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|---|---|---|---|---|
| US6410664B1 (en) * | 1997-03-24 | 2002-06-25 | Cryovac, Inc. | Catalyst compositions and processes for olefin polymers and copolymers |
| CN1328879A (en) * | 2001-06-26 | 2002-01-02 | 中国科学院长春应用化学研究所 | Preparation method of self-solidified 'after cyclopentadiene' nickel base olefinic polymerization catalyst |
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