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CN1302018C - Olefin polymerization catalyst coordinated by [C N] type bidentate ligand and late transition metal and preparation method thereof - Google Patents

Olefin polymerization catalyst coordinated by [C N] type bidentate ligand and late transition metal and preparation method thereof Download PDF

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CN1302018C
CN1302018C CNB2004100931211A CN200410093121A CN1302018C CN 1302018 C CN1302018 C CN 1302018C CN B2004100931211 A CNB2004100931211 A CN B2004100931211A CN 200410093121 A CN200410093121 A CN 200410093121A CN 1302018 C CN1302018 C CN 1302018C
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catalyst
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ligand
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olefin polymerization
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CN1644592A (en
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金国新
王昕�
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Fudan University
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Abstract

The invention belongs to the technical field of catalysts, and particularly relates to 'after-cyclopentadiene' [ CN]An olefin polymerization catalyst with coordination of a type bidentate ligand and a late transition metal, a preparation method thereof and application thereof in catalyzing norbornene polymerization reaction. The expression of the catalyst is [ L-M]L represents a ligand containing C, N atoms coordinated to the metal, and M represents one of Ni, Pd or Pt metals. The preparation process comprises reacting methanol, acetone, etc. as solvent with 2-methyl chloropyridine and 1-alkyl imidazole as raw materials to obtain ligand, reacting the ligand with silver oxide to obtain argentum compound, and reacting the argentum compound with [ M (PPh)3)2X2]The catalyst is prepared by reaction, and is matched with a cocatalyst MAO or MMAO for norbornene polymerization reaction, so that the catalyst has high catalytic activity. The catalyst is simple to prepareGood stability, and can obtain polynorbornene product with high molecular weight, high glass transition temperature and unique property.

Description

Olefin polymerization catalysis of [C^N] type bitooth ligand and post transition metal coordination and preparation method thereof
Technical field
The invention belongs to catalyst preparation technical field, be specifically related to the olefin polymerization catalysis and preparation method thereof and the application in the polynorbornene preparation of a kind of [C^N] type part and post transition metal coordination.
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 have appearred in short 50 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 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, big 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, wherein the fastest with the nickel catalyst development.
Since Arduengo in 1999 isolates first free Cabbeen; N-heterocyclic carbine has caused extensive interest in the organometallic catalytic field as part, for example in hydrogenation, hydrogenation formyl reaction, hydrosilation reaction, ammonia hydrogenation, C-C linked reaction and olefin metathesis reactions application is arranged all.In recent years, the bidentate and the polydentate ligand that had not only contained strong donor residues but also contained weak donor residues (half unstable base) are used more and more wider in homogeneous catalysis system, mainly be because half unstable base in this class part is easy to dissociate from metal center, producing the coordination room is convenient to the substrate coordination and gets on, and meanwhile, strong donor residues still keeps the coordination with metal.Therefore this class contains half unstable basic N-heterocyclic carbine compound and once was used for the copolymerization of catalysis C-C coupling and norbornylene and CO, but but rarely has application for the olefinic polymerization aspect.
Summary of the invention
The purpose of this invention is to provide a kind of preparation cost is low, catalytic activity is high [C^N] type part and olefin polymerization catalysis of post transition metal coordination and preparation method thereof and the application in the polynorbornene preparation.
The olefin polymerization catalysis that the present invention proposes, under the anhydrous and oxygen-free condition, with acetone, methylene dichloride, ether or methyl alcohol is solvent, is starting raw material by 2-picoline chlorine, 1-alkyl imidazole, makes ligand L-3-alkyl-picolyl imidazoles halogenation q salt through reaction; The silver suboxide reaction of ligand L and 2.3-2.8 times molar weight obtains patina thing Ag-L; [M (the PPh of patina thing and equimolar amount 3) 2X 2] carry out metal exchange reaction and obtain described catalyzer.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 catalyzer expression formula of the present invention preparation is [L-M], L represent a kind of contain can with the C of metal-complexing, the part of N atom, M represents a kind of of metal Ni, Pd or Pt, concrete structure is shown below:
Wherein, M is a kind of of central metal Ni, Pd, Pt; R is CH 3, i-Pr, t-Bu or CH 2Ph; X is Cl or Br.
The olefin polymerization catalysis preparation process of [C^N] type bitooth ligand and post transition metal coordination is as follows:
(1) preparation of 2-picoline chlorine
The structural formula of 2-picoline chlorine is:
Figure C20041009312100042
The 10-100mL2-picoline, 60-600mL Glacial acetic acid, the H of 10-100mL30% 2O 2In 70-80 ℃ of reaction 2-4 hour, at the H that adds 7.2-72mL30% 2O 2More than 12 hours, the mixed solution normal pressure concentrates down, distillation in the 70-80 reaction, until steaming the 60-600mL cut, interior temperature is not higher than 145 ℃, and then adds 20-200mL water, concentrates out the 24-240mL cut once again, underpressure distillation then, do not flow out to there being obvious liquid, raffinate is transferred in the beaker, use 20-200mlH 2O washing reaction bottle repeatedly makes and shifts fully, and stir on the limit, and the limit adds Na 2CO 3Be neutralized to no bubble and emerge, with 20-200mL * 4CH 2Cl 2Extraction merges CH 2Cl 2Layer is used anhydrous MgSO 4Drying is removed solvent, the raffinate underpressure distillation, and the cut of 90 ℃/2mmHg of collection obtains the 2.64-26.4g white solid after the cooling.Above product is added in the 100-1000ml single port bottle, add 12-120mL benzene again, 4.6-46g4-Methyl benzenesulfonyl chlorine stirred 3 hours, removed solvent, obtained dark oily matter, vacuumized, towards N 2, slowly heating keeps oil bath temperature at 120-125 ℃, reacted 3 hours, cooling adds the 8-80mL ether, be heated to backflow, cooling, supernatant liquid inclines, repeatedly twice, in reaction flask, add 20-2000mL water then, mixed solution is transferred in the beaker, wash reaction flask again with water, be abundant transfer, stir on the limit, and the limit adds NaHCO 3Not emerging to there being bubble in middle river, adds the 40-400mL ether, fully stirs, and filters, and the upper strata is got in the filtrate layering, and water layer does not have color with extracted with diethyl ether to ether layer, and combined ether layer is with anhydrous that Na 2SO 4Drying is removed solvent, obtains the 2-20g red oil.
(2) preparation of 1-isopropylimdazole:
1-isopropylimdazole structural formula is:
Figure C20041009312100051
To be acidified to the Isopropylamine (0.10-1mol) of PH=2 with phosphoric acid, 40% oxalic dialdehyde (0.10-1mol), 40% formaldehyde (0.10-1mol) stirred 20-60 minute, temperature is raised to 85-100 ℃ then, in 20-60 minute, drip saturated ammonium chloride solution (0.1-1mol), under this temperature, continue to stir 40-80 minute, reaction is cooled to room temperature, regulate PH=12～13 with NaOH again, extract repeatedly (being generally 3-6 time) with ether then, combining extraction liquid is used anhydrous MgSO 4Drying is filtered, and takes out solvent, last underpressure distillation, and the cut of getting 60 ℃ (100Pa) is the 1-isopropylimdazole.
(3) preparation of 1-t-butyl imidazole:
1-t-butyl imidazole structural formula is:
Figure C20041009312100052
To be acidified to the TERTIARY BUTYL AMINE (0.20-2mol) of PH=2,40% oxalic dialdehyde (0.20-2mol), 40% formaldehyde (0.20-2mol) with phosphoric acid, stirred 20-60 minute, temperature is raised to 85-100 ℃ then, in 2-4 hour, drips saturated ammonium chloride solution (0.2-2mol), under this temperature, continue to stir 40-80 minute, reaction is cooled to room temperature, regulate PH=12～13 with NaOH again, extract with ether then, extraction is (general 3-6 time) repeatedly, combining extraction liquid is used anhydrous MgSO 4Drying is filtered, and takes out solvent, last underpressure distillation, and the cut of getting 82 ℃ (140Pa) is the 1-t-butyl imidazole.
(4) preparation of 3-methyl-picolyl imidazole salts:
3-methyl-picolyl imidazole salts structure is:
With picoline chlorine (5-50mmol), 1-Methylimidazole (5-50mmol), NaI (5-50mmol), the mixture of 20-200mL acetone stirred 40-60 hour, filtered, and drained solvent and obtained brown oily matter, brown oil is dissolved in the methylene dichloride again, and adularescent insolubles (NaCl) is crossed and is filtered out (NaCl), add ether in the filtrate, the red oil that settles out is dissolved in red oil in the methylene dichloride again, uses the ether recrystallization, obtain red solid, drain and weigh.
(5) preparation of 3-sec.-propyl-picolyl imidazole salts:
3-sec.-propyl-picolyl imidazole salts structural formula is:
With picoline chlorine (1-10mmol), 1-isopropylimdazole (1-10mmol), NaI (1-10mmol), the mixture of 20-200mL acetone stirred 40-60 hour, filtered, and drained solvent and obtained brown oily matter, brown oil is dissolved in the methylene dichloride again, and adularescent insolubles (NaCl) is crossed and is filtered out (NaCl), add ether in the filtrate, the red oil that settles out is dissolved in red oil in the methylene dichloride again, uses the ether recrystallization, obtain red solid, drain and weigh.
(6) preparation of the 3-tertiary butyl-picolyl imidazole salts:
The 3-tertiary butyl-picolyl imidazole salts structural formula is:
With picoline chlorine (1-10mmol), 1-t-butyl imidazole (1-10mmol), NaI (1-10mmol), the mixture of 20-200mL acetone stirred 40-60 hour, filtered, and drained solvent and obtained brown oily matter, brown oil is dissolved in the methylene dichloride again, and adularescent insolubles (NaCl) is crossed and is filtered out (NaCl), add ether in the filtrate, the red oil that settles out is dissolved in red oil in the methylene dichloride again, uses the ether recrystallization, obtain red solid, drain and weigh.
(7) preparation of 3-benzyl-picolyl imidazole salts:
3-benzyl-picolyl imidazole salts structural formula is:
Figure C20041009312100072
With picoline chlorine (1-10mmol), 1-benzyl imidazole (1-10mmol), NaI (1-10mmol), the mixture of 20-200mL acetone stirred two days, filtered, and drained solvent and obtained brown oily matter, brown oil is dissolved in the methylene dichloride again, and adularescent insolubles (NaCl) is crossed and is filtered out (NaCl), add ether in the filtrate, the red oil that settles out is dissolved in red oil in the methylene dichloride again, uses the ether recrystallization, obtain red solid, drain and weigh.
In the above-mentioned steps, (1)-(3) make starting raw material, and (4)-(7) make various parts respectively.
(8) with the preparation of [C^N] type bitooth ligand coordinate rear transition metal nickel catalyzator:
Its structural formula is:
Carry out under the protection of Preparation of catalysts and high pure nitrogen anhydrous in anaerobic.The part of 1-20mol is dissolved in the anhydrous CH of 20-400 milliliter 2Cl 2In, add 2.5-50mmolAg 2O (silver suboxide) at room temperature stirred 2-3 hour, and the mixed solution with reaction filters then, and filtrate being added drop-wise to contained 1-20mmol[Ni (PPh 3) 2Cl 2] CH 2Cl 2In the solution; After at room temperature stirring 12-16 hour, filter, gained solid dissolve with methanol refilters, and filtrate adds a large amount of ether so that precipitation is separated out; After vacuum filtration removed and desolvates, precipitation with ether washing 3-5 time, was drained vacuum-drying again, obtains catalyzer, productive rate 68%-77%.
The building-up process of catalyzer of the present invention is as follows shown in the formula:
Figure C20041009312100082
Wherein, R is CH 3, i-Pr, t-Bu or CH 2Ph.
Especially, work as M=Ni, R=CH 3The time, the crystalline structure of catalyzer is as shown in Figure 1.Work as M=Ni, R=CH 2During Ph, the crystalline structure of catalyzer as shown in Figure 2.
Use catalyzer of the present invention to carry out catalysis norbornylene polyaddition reaction, concrete steps are as follows:
The norbornylene addition polymerization is carried out under the anhydrous and oxygen-free condition.Nitrogen atmosphere adds the chlorobenzene solution 0.2-2 μ mol that contains the above-mentioned catalyzer of 2-20mL (A component) successively with syringe down in polymerization bottle, stir to add down and contain the chlorobenzene solution 20-200mmol of 3-30mL norbornylene and the chlorobenzene of 3-30mL, under 0-100 ℃ of temperature, keep 5-10min, the toluene solution that adds 0.066-1.32mL promotor (B component) MAO (methylaluminoxane) or MMAO (modified methylaluminoxane), in the promotor, Al: Ni=500-10000: 1, more excellent Al: Ni=500-5000: 1, initiated polymerization, the cumulative volume of reaction system generally remains on 10-100mL (adjusting of different volumes useable solvents chlorobenzene), behind the reaction 8-12min, pour mixture in the acidifying ethanolic soln (ethanol/HCl Conc=95: 5).With polymer filtration, and with washing with alcohol 2-4 time, 75-90 ℃ following vacuum-drying 40-60 hour.The active amt level is 10 6~ 10 7G PNB/ (mol Nih), the molecular weight of polyethylene order of magnitude is 10 6G/mol.
Description of drawings
Fig. 1 is a kind of crystalline structure diagram of catalyzer of the present invention.
Fig. 1 is the another kind of crystalline structure diagram of catalyzer of the present invention.
Embodiment
The invention is further illustrated by the following examples.
The preparation of embodiment 1:2-picoline chlorine
Add 25mL2-picoline, 150mL Glacial acetic acid, the H of 25mL30% in the 250mL three-necked bottle 2O 2In 70 ~ 80 ℃ of reaction 3h, at the H that adds 18mL30% 2O 2, spending the night in 70 ~ 80 reactions, the mixed solution normal pressure concentrates down, distillation, until steaming the 150mL cut, interior temperature is not higher than 145 ℃, and then adds 50mL water, concentrates out the 60mL cut once again, underpressure distillation is not then flowed out to there being obvious liquid, and raffinate is transferred in the 250mL beaker, uses 50mlH 2O washing reaction bottle twice makes and shifts fully, and stir on the limit, and the limit adds Na 2CO 3Be neutralized to no bubble and emerge, with 50mL * 4CH 2Cl 2Extraction merges CH 2Cl 2Layer is used anhydrous MgSO 4Drying is removed solvent, the raffinate underpressure distillation, and the cut of 90 ℃/2mmHg of collection obtains the 6.57g white solid after the cooling.Above product is added in the 250ml single port bottle, add 30mL benzene again, 11.5g4-Methyl benzenesulfonyl chlorine stirs 3h, removes solvent, obtains dark oily matter, vacuumizes, towards N 2, slowly heating keeps oil bath temperature at 120 ~ 125 ℃, reaction 3h, if cooling is the 20mL ether, be heated to backflow, cooling, supernatant liquid inclines, repeatedly twice, in reaction flask, add 50mL water then, mixed solution is transferred in the beaker, use 50mL water washing reaction flask again, be abundant transfer, stir on the limit, and the limit adds NaHCO 3Not emerging to there being bubble in middle river, adds the 100mL ether, fully stirs, and filters, and the upper strata is got in the filtrate layering, and water layer does not have color with extracted with diethyl ether to ether layer, and combined ether layer is with anhydrous that Na 2SO 4Drying is removed solvent, obtains the 5.14g red oil.
The preparation of embodiment 2:1-isopropylimdazole:
Will with phosphoric acid be acidified to PH=2 Isopropylamine (8.7mL, 0.10mol), 40% oxalic dialdehyde (11.5mL, 0.10mol), 40% formaldehyde (7.5mL, 0.10mol), stir after half an hour, slowly temperature is raised to 95 ℃, in one and a half hours, drip saturated ammonium chloride solution (0.1mol), after continuing to stir one hour under this temperature, reaction is cooled to room temperature, regulate PH=12～13 with NaOH again, extract with ether then, extract 5 times, combining extraction liquid is used anhydrous MgSO 4Drying is filtered, and takes out solvent, last underpressure distillation, and the cut of getting 60 ℃ (100Pa) is 2 isopropyl imidazole.
The preparation of embodiment 3:1-t-butyl imidazole:
Will with phosphoric acid be acidified to PH=2 TERTIARY BUTYL AMINE (21.2mL, 0.20mol), 40% oxalic dialdehyde (23mL, 0.20mol), 40% formaldehyde (15mL, 0.20mol), stir after half an hour, slowly temperature is raised to 95 ℃, in three hours, drip saturated ammonium chloride solution (0.2mol), after continuing to stir one hour under this temperature, reaction is cooled to room temperature, regulate PH=12～13 with NaOH again, extract with ether then, extract 5 times, combining extraction liquid is used anhydrous MgSO 4Drying is filtered, and takes out solvent, last underpressure distillation, and the cut of getting 82 ℃ (140Pa) is the 2-t-butyl imidazole.
The preparation of embodiment 4:3-methyl-picolyl imidazole salts:
With picoline chlorine (743mg, 5.85mmol), 1-Methylimidazole (0.47mL, 5.89mmol), NaI (0.88g, 5.9mmol), the mixture of 20mL acetone stirred two days, filter, drain solvent and obtain brown oily matter, be dissolved in brown oil in the methylene dichloride again, adularescent insolubles (NaCl), cross and filter out (NaCl), add ether in the filtrate, red oil settles out, again red oil is dissolved in the methylene dichloride, use the ether recrystallization, obtain red solid, drain the 1.22g that weighs (69%).
The preparation of embodiment 5:3-sec.-propyl-picolyl imidazole salts:
With picoline chlorine (1.27g, 10mmol), 1-isopropylimdazole (1.1g, 10mmol), and NaI (1.50g, 10mmol), the mixture of 200mL acetone stirred two days, filtered, and drained solvent and obtained brown oily matter, brown oil is dissolved in the methylene dichloride again, and adularescent insolubles (NaCl) is crossed and is filtered out (NaCl), add ether in the filtrate, the red oil that settles out is dissolved in red oil in the methylene dichloride again, use the ether recrystallization, obtain red solid, drain and weigh.
The preparation of the embodiment 6:3-tertiary butyl-picolyl imidazole salts:
With picoline chlorine (1.27g, 10mmol), 1-t-butyl imidazole (1.1g, 10mmol), and NaI (1.50g, 10mmol), the mixture of 200mL acetone stirred two days, filtered, and drained solvent and obtained brown oily matter, brown oil is dissolved in the methylene dichloride again, and adularescent insolubles (NaCl) is crossed and is filtered out (NaCl), add ether in the filtrate, the red oil that settles out is dissolved in red oil in the methylene dichloride again, use the ether recrystallization, obtain red solid, drain and weigh.
The preparation of embodiment 7:3-benzyl-picolyl imidazole salts:
With picoline chlorine (1.27g, 10mmol), 1-benzyl imidazole (1.1g, 10mmol), and NaI (1.50g, 10mmol), the mixture of 200mL acetone stirred two days, filtered, and drained solvent and obtained brown oily matter, brown oil is dissolved in the methylene dichloride again, and adularescent insolubles (NaCl) is crossed and is filtered out (NaCl), add ether in the filtrate, the red oil that settles out is dissolved in red oil in the methylene dichloride again, use the ether recrystallization, obtain red solid, drain and weigh.
Embodiment 8: with the preparation of [C^N] type bitooth ligand coordinate rear transition metal nickel catalyzator:
Change under the protection of the preparation of agent and high pure nitrogen anhydrous and carry out in anaerobic.Part among the embodiment 4 (10mmol) is dissolved in the anhydrous CH of 200 milliliters processing 2Cl 2In, add Ag 2After O (25mmol) at room temperature stirred 2-3 hour, with the mixed solution filtration of reaction, filtrate is added drop-wise at leisure contained 1Ommol[Ni (PPh 3) 2Cl 2] CH 2Cl 2In the solution.After at room temperature stirring 12-16 hour, filter, gained solid dissolve with methanol refilters, and filtrate adds a large amount of ether so that precipitation is separated out.After vacuum filtration removed and desolvates, precipitation with ether washing 3-5 time, was drained vacuum-drying again, obtains the catalyst A component, productive rate 68%-77%.
Embodiment 9: with the preparation of [C^N] type bitooth ligand coordinate rear transition metal nickel catalyzator:
Change under the protection of the preparation of agent and high pure nitrogen anhydrous and carry out in anaerobic.Part among the embodiment 5 (15mmol) is dissolved in the anhydrous CH of 400 milliliters processing 2Cl 2In, add Ag 2After O (46mmol) at room temperature stirred 2-3 hour, with the mixed solution filtration of reaction, filtrate is added drop-wise at leisure contained 15mmol[Ni (PPh 3) 2Cl 2] CH 2Cl 2In the solution.After at room temperature stirring 12-16 hour, filter, gained solid dissolve with methanol refilters, and filtrate adds a large amount of ether so that precipitation is separated out.After vacuum filtration removed and desolvates, precipitation with ether washing 3-5 time, was drained vacuum-drying again, obtains the catalyst A component, productive rate 68%-77%.
Embodiment 10: with the preparation of [C^N] type bitooth ligand coordinate rear transition metal nickel catalyzator:
Carry out under the protection of Preparation of catalysts and high pure nitrogen anhydrous in anaerobic.Part among the embodiment 6 (1mmol) is dissolved in the anhydrous CH of 20 milliliters processing 2Cl 2In, add Ag 2After O (2.5mmol) at room temperature stirred 2-3 hour, with the mixed solution filtration of reaction, filtrate is added drop-wise at leisure contained 1mmol[Ni (PPh 3) 2Cl 2] CH 2Cl 2In the solution.After at room temperature stirring 12-16 hour, filter, gained solid dissolve with methanol refilters, and filtrate adds a large amount of ether so that precipitation is separated out.After vacuum filtration removed and desolvates, precipitation with ether washing 3-5 time, was drained vacuum-drying again, obtains the catalyst A component, productive rate 68%-77%.
Embodiment 11: with the preparation of [C^N] type bitooth ligand coordinate rear transition metal nickel catalyzator:
Carry out under the protection of Preparation of catalysts and high pure nitrogen anhydrous in anaerobic.Part among the embodiment 7 (20mmol) is dissolved in the anhydrous CH of 200 milliliters processing 2Cl 2In, add Ag 2After O (50mmol) at room temperature stirred 2-3 hour, with the mixed solution filtration of reaction, filtrate is added drop-wise at leisure contained 20mmol[Ni (PPh 3) 2Cl 2] CH 2Cl 2In the solution.After at room temperature stirring 12-16 hour, filter, gained solid dissolve with methanol refilters, and filtrate adds a large amount of ether so that precipitation is separated out.After vacuum filtration removed and desolvates, precipitation with ether washing 3-5 time, was drained vacuum-drying again, obtains the catalyst A component, productive rate 68%-77%.
Embodiment 12: catalysis norbornylene polyaddition reaction:
Nitrogen atmosphere adds down the chlorobenzene solution (0.2 μ molNi) of the catalyzer (A component) that 2.0mL embodiment 8 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, (1000: the 1Al/Ni) toluene solution of cocatalyst B component MAO, initiated polymerization, the cumulative volume of reaction system generally remain on 10mL (adjusting of different volumes useable solvents chlorobenzene) to add 0.132mL, 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, activity is 3.3 * 10 5G PNB/ (mol Nih).
Embodiment 13: catalysis norbornylene polyaddition reaction:
Norbornene polymerization is operated with embodiment 12, catalyzer (A component) the 0.2 μ mol (pressing Al/Ni=1700) of methylaluminoxane (MAO) 0.265mL, embodiment 8 preparations, and activity is 1.28 * 10 6G PNB/ (mol Nih).
Embodiment 14: catalysis norbornylene polyaddition reaction:
The norbornene polymerization operation is with embodiment 12, and catalyzer (A component) 0.2 μ mol (by the Al/Ni=5000) activity of methylaluminoxane (MAO) 0.397mL, embodiment 8 preparations is 2.55 * 10 6G PNB/ (mol Nih).
Embodiment 15: catalysis norbornylene polyaddition reaction:
Converging operation is with embodiment 14, and polymerization temperature is 20 ℃, and activity is 3.5 * 10 6G PNB/ (mol Nih), productive rate is 12%.
Embodiment 16: catalysis norbornylene polyaddition reaction:
Converging operation is with embodiment 14, and polymerization temperature is 30 ℃, and activity is 4.0 * 10 6G PNB/ (mol Nih), molecular weight is 4.2 * 10 6G/mol, productive rate are 15%.
Embodiment 17: catalysis norbornylene polyaddition reaction:
Converging operation is with embodiment 14, and polymerization temperature is 40 ℃, and active 1.56 * 10 7G PNB/ (mol Nih), productive rate is 55%.
Embodiment 18: catalysis norbornylene polyaddition reaction:
Converging operation is with embodiment 14, and polymerization temperature is 60 ℃, and active 1.65 * 10 7G PNB/ (mol Nih), molecular weight is 2.6 * 10 6G/mol, productive rate are 59%.
Embodiment 19: catalysis norbornylene polyaddition reaction:
Converging operation is with embodiment 14, and polymerization temperature is 60 ℃, and active 2.6 * 10 7G PNB/ (mol Nih), molecular weight is 1.3 * 10 6G/mol, productive rate are 92%.
Embodiment 20: catalysis norbornylene polyaddition reaction:
Converging operation is with embodiment 14, and polymerization temperature is 80 ℃, and active 2.17 * 10 7G PNB/ (mol Nih), molecular weight is 1.1 * 10 6G/mol, productive rate are 77%.
Embodiment 21: catalysis norbornylene polyaddition reaction:
Converging operation is with embodiment 16, and polymerization time is 30min, and active 3.0 * 10 6G PNB/ (mol Nih), productive rate is 32%.
Embodiment 22: catalysis norbornylene polyaddition reaction:
Converging operation is with embodiment 16, and polymerization time is 60min, and active 2.3 * 10 6G PNB/ (mol Nih), productive rate is 48%.
Embodiment 23: catalysis norbornylene polyaddition reaction:
Converging operation is with embodiment 16, and polymerization time is 120min, and active 1.3 * 10 6G PNB/ (mol Nih), productive rate is 56%.
Embodiment 24: catalysis norbornylene polyaddition reaction:
Nitrogen atmosphere adds down the chlorobenzene solution (0.2 μ molNi) of the catalyzer (A component) that 2.0mL embodiment 11 makes successively in Schl enk 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, (5000: the 1Al/Ni) toluene solution of promotor (B component) MAO, initiated polymerization, the cumulative volume of reaction system generally remain on 10mL (adjusting of different volumes useable solvents chlorobenzene) to add 0.397mL, 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, activity is 5.3 * 10 6G PNB/ (mol Nih).

Claims (3)

1、一类[C^N]型双齿配体与后过渡金属镍配位的烯烃聚合催化剂，其特征在于组分表达式为[L2M]，L表示一种含有可与金属配位的C，N原子的双齿配体，M表示金属Ni，Pd或Pt，具体结构如下式所示：1. A class of olefin polymerization catalysts in which [C^N]-type bidentate ligands coordinate with late-transition metal nickel, which is characterized in that the composition expression is [L 2 M], and L represents a compound containing The bidentate ligands of C and N atoms, M represents metal Ni, Pd or Pt, and the specific structure is shown in the following formula: 其中M为中心金属Ni、Pd、Pt之一种；R为CH3，i-Prt，t-Bu或CH2Ph；X为Cl或Br；此类烯烃聚合催化剂制备过程如下：Where M is one of the central metals Ni, Pd, and Pt; R is CH 3 , i-Prt, t-Bu or CH 2 Ph; X is Cl or Br; the preparation process of this type of olefin polymerization catalyst is as follows: 在无水无氧条件下，以丙酮、二氯甲烷、乙醚或甲醇为溶剂，由2-甲基氯吡啶、1-烷基咪唑为起始原料，经反应制得配体L-3-烷基-甲基吡啶基咪唑卤化鎓盐；配体L与23倍摩尔量的氧化银反应得到银化物Ag-L；银化物再和等摩尔量的[M(PPh3)2X2]进行金属交换反应，经过萃取、过滤、洗涤等，抽真空干燥得到相应的催化剂。Under anhydrous and oxygen-free conditions, using acetone, dichloromethane, ether or methanol as a solvent, starting from 2-methylchloropyridine and 1-alkylimidazole, the ligand L-3-alkane is prepared by reaction base -picoline imidazolium halide salt; the ligand L reacts with 23 times the molar amount of silver oxide to obtain the silver compound Ag- L ; Exchange reaction, after extraction, filtration, washing, etc., vacuum drying to obtain the corresponding catalyst. 2、一种如权利要求1所述的[C^N]型双齿配体与后过渡金属配位的烯烃聚合催化剂的制备方法，其特征在于：在无水无氧条件下，以丙酮、二氯甲烷、乙醚或甲醇为溶剂，由2-甲基氯吡啶、1-烷基咪唑为起始原料，经反应制得配体L-3-烷基甲基吡啶基咪唑卤化翁盐；配体L与2-3倍摩尔量的氧化银反应得到银化物Ag-L；银化物再和等摩尔量的[M(PPh3)2X2]进行金属交换反应，经过萃取、过滤、洗涤和抽真空干燥，得到相应的[C^N]型配体与后过渡金属配位的烯烃聚合催化剂，M为中心金属Ni、Pd或Pt之一种。2. A method for preparing an olefin polymerization catalyst coordinated by a [C^N] type bidentate ligand and a late transition metal as claimed in claim 1, characterized in that: under anhydrous and oxygen-free conditions, use acetone, Dichloromethane, ether or methanol as a solvent, 2-methylchloropyridine and 1-alkylimidazole as starting materials, react to prepare the ligand L-3-alkylmethylpyridylimidazole halide; The silver compound Ag-L is obtained by reacting the body L with 2-3 times the molar amount of silver oxide; the silver compound is then subjected to a metal exchange reaction with an equimolar amount of [M(PPh 3 ) 2 X 2 ], after extraction, filtration, washing and Vacuum-dry to obtain the corresponding olefin polymerization catalyst in which [C^N]-type ligands coordinate with late transition metals, and M is one of central metal Ni, Pd or Pt. 3、一种如权利要求1所述烯烃聚合催化剂在催化降冰片烯加成聚合反应中的应用，其特征在于：3. The application of an olefin polymerization catalyst as claimed in claim 1 in catalytic norbornene addition polymerization, characterized in that: 降冰片烯加成聚合在无水无氧条件下进行，氮气氛围下用注射器向聚合瓶中依次加入含2-20mL所述催化剂的氯苯溶液0.2-2μmol，搅拌下加入含3-30mL降冰片烯的氯苯溶液20-200mmol和3-30mL的氯苯，在0-100℃温度下，保持5-10分钟，加入0.066-1.32mL助催化剂MAO或MMAO的甲苯溶液，助催化剂中，Al∶Ni＝500-10000∶1，引发聚合反应，反应体系的总体积保持在10-100mL，反应8-12分钟后，将混合物倒入酸化的乙醇溶液中，将聚合物过滤，并用乙醇洗涤2-4次，75-90℃下真空干燥40-60小时。Addition polymerization of norbornene is carried out under anhydrous and oxygen-free conditions. Under nitrogen atmosphere, add 0.2-2μmol of chlorobenzene solution containing 2-20mL of the catalyst into the polymerization bottle successively with a syringe, and add 3-30mL of norbornene under stirring. Chlorobenzene solution of 20-200mmol and 3-30mL of chlorobenzene, at a temperature of 0-100°C, keep for 5-10 minutes, add 0.066-1.32mL of cocatalyst MAO or MMAO toluene solution, in cocatalyst, Al: Ni=500-10000:1, initiate the polymerization reaction, keep the total volume of the reaction system at 10-100mL, after reacting for 8-12 minutes, pour the mixture into acidified ethanol solution, filter the polymer, and wash with ethanol for 2- 4 times, vacuum dry at 75-90°C for 40-60 hours.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US6410664B1 (en) * 1997-03-24 2002-06-25 Cryovac, Inc. Catalyst compositions and processes for olefin polymers and copolymers

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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