CN105254786B - A kind of C C bridgings [ONNO] β ketimides metallic catalyst and preparation method - Google Patents
A kind of C C bridgings [ONNO] β ketimides metallic catalyst and preparation method Download PDFInfo
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Abstract
A kind of C C bridgings [ONNO] β ketimides metallic catalyst and preparation method, its general structure is：Wherein, M=Ni, Pd, Co, Fe or Cu；R1、R2、R3For corresponding alkyl.Preparation method includes：(I) preparation of β ketimides part；(II) preparation of major catalyst C C bridgings [ONNO] β ketimide metallic catalysts.Copolymer of the present invention in catalyst ENB and norbornene derivative has high light transmittance, high glass-transition temperature, good heat endurance, oxidation stability, low hydroscopicity, low dielectric constant and good processing, dissolving and adhesion property.
Description
Technical field
The invention belongs to catalyst and preparing technical field, more particularly to for ENB and norbornene derivative
The major catalyst and preparation method of the catalyst system and catalyzing of addition copolymerization.
Background technology
With industrial expansion, polycyclic alkene material has obtained extensive concern by its excellent performance.ENB
It is a kind of typical cyclic olefin material, it has three kinds of polymerization methodses：(1) ring-opening metathesis polymerization, the production that this polymerization methodses are obtained
Contain double bond in owner's chain, be a kind of polymerization methodses of current most study；(2) cation or radical polymerization, this mode
It is that monomer is connected by 2,7-, but can only obtain the relatively low oligomer of molecular weight；(3) vinyl add-on type polymerize, this
Polymerization methodses are to open the addition polymerization carried out by double bond, in main chain containing twin nuclei (US Patent 5468819,
5569730).The ENB homopolymer of wherein add-on type has good optical property, heat endurance, chemical stability, low
Hydroscopicity and dielectric constant, be a kind of good polymeric material, but be due to its crisp matter and processing characteristics and dissolubility
Can be poor, so its application in the industry is greatly limited.So we need to prepare the ENB of functionalization
Improve it while its original advantage is retained not enough.
The optimization of catalyst system and catalyzing has vital meaning to improving functional poly ENB combination property, therefore opens
The catalyst system and catalyzing for sending out efficient stable is particularly significant for developing functional poly ENB.It is catalyzed urging for norbornene polymerization
The major catalyst of change system is mainly metal complex, generally can be divided into Ziegler-Natta catalyst, metallocene catalyst,
Late transition metal is catalyzed and rare-earth metal catalyst.Wherein in the metal of Ziegler-Natta catalyst and metallocene catalyst
The heart is early transition metal, and the tolerance to polar monomer is poor, active relatively low when being catalyzed polarity norbornene monomer.Cross afterwards
Metallic catalyst is crossed to the tolerance of polar group preferably, and synthesis is simple, to the catalytic activity of polarity norbornene monomer compared with
Height, is a kind of preferable catalyst.We have done certain relevant work (China are specially in the development of late transition metal catalyst
Sharp application number：201110299869.7,201110299867.8).
The content of the invention
It is an object of the invention to provide a kind of C-C bridgings [ONNO]-beta-ketimine metallic catalyst and preparation method, sheet
The catalyst of invention can prepare with high light transmittance, high glass-transition temperature, good heat endurance, oxidation stability,
Low hydroscopicity, low dielectric constant and good processing characteristics, the ENB of solubility property and adhesion property and drop ice
The copolymer of piece ene derivative.
Catalyst of the present invention is a kind of C-C bridgings [ONNO]-beta-ketimine metal complex, is by β -one and contains
α-H aromatic amine and the prewired body of trans metal are prepared, the C-C bridged linkages for possessing uniqueness, and metal active centres are in
[ONNO] four-coordination type.Catalyst of the present invention mainly has C-C bridgings [ONNO]-beta-ketimine nickel (II), C-C bridgings
[ONNO]-beta-ketimine palladium (II), C-C bridgings [ONNO]-beta-ketimine cobalt (II), C-C bridgings [ONNO]-beta-ketimine iron
Or C-C bridgings [ONNO]-beta-ketimine copper (II) complex etc. (II).Its general structure is：
Wherein, M=Ni, Pd, Co, Fe or Cu.
R1、R2、R3It can be respectively situations below：
(1)R1=CH3, R2=CH3, R3=
(2)R1=CH3, R2=CF3, R3=
(3)R1=CH3, R2=R3=
(4)R1=CH3, R2=CH3, R3=
(5)R1=CH3, R2=CF3, R3=
(6)R1=CH3, R2=R3=
(7)R1=CH3, R2=CH3, R3=
(8)R1=CH3, R2=CF3, R3=
(9)R1=CH3, R2=R3=
(10)R1=CH3, R2=CH3, R3=
(11)R1=CH3, R2=CF3, R3=
(12)R1=CH3, R2=R3=
(13)R1=CH2CH(CH3)2, R2=CH3, R3=
(14)R1=CH2CH(CH3)2, R2=CH3, R3=
(15)R1=CH2CH(CH3)2, R2=CH3, R3=
(16)R1=CH2CH(CH3)2, R2=CH3, R3=
(17)R1=CF3, R2=CF3, R3=
(18)R1=CF3, R2=R3=
(19)R1=CF3, R2=CF3, R3=
(20)R1=CF3, R2=R3=
(21)R1=CF3, R2=CF3, R3=
(22)R1=CF3, R2=R3=
(23)R1=CF3, R2=CF3, R3=
(24)R1=CF3, R2=R3=
(25)R1=R2=R3=
(26)R1=R2=R3=
(27)R1=R2=R3=
(28)R1=R2=R3=
The preparation method of C-C bridgings [ONNO]-beta-ketimine metallic catalyst of the present invention, comprises the following steps：
(I) preparation of beta-ketimine part.
It is 1 that mol ratio is added in the reaction bulb equipped with reflux condensing tube and water knockout drum:1 beta-diketon and the virtue of-H containing α
Fragrant amine, and catalytic amount glacial acetic acid and 50-300mL ethanol, reaction 8-48 hour after, with n-hexane recrystallize or depressurize steaming
Evaporate and obtain purity up to more than 95% beta-ketimine part.
(II) preparation of major catalyst C-C bridgings [ONNO]-beta-ketimine metallic catalyst.
NaH is added in the tetrahydrofuran containing beta-ketimine part (THF) solution under nitrogen atmosphere, NaH and β -one
The molar ratio of imine ligand is 1:2,4-8h is stirred at room temperature, the pre- part of trans metal of 1/2 equivalent is added afterwards, at room temperature
8-12h is persistently stirred, filters, is recrystallized to give C-C bridgings [ONNO] beta-ketimine metal complex.
Metal complex is main by its electronic effect and three-dimensional effect as the activity of catalyst, stability and selectivity
Influence.Strong electron-withdrawing group group is introduced generally in its structure to strengthen its electronic effect, such as arene group；And generally change
The space for becoming metal complex founds structure to strengthen three-dimensional effect, and then the catalytic activity and its stability of enhancing metal complex,
Such as introduce bridged group.The introducing of abutment improves the structural stability of bridging catalyst, converts the big I of group of abutment
To regulate and control the steric hindrance in catalytic active center space, so that stereoselectivity when effectively regulating and controlling catalytic activity and polymerization, improves
The steric regularity and molecular weight of polymer.
C-C bridgings [ONNO] of the present invention-beta-ketimine metallic catalyst catalysis ENB and ENB spread out
Biological copolymer has high light transmittance, high glass-transition temperature, good heat endurance, oxidation stability, low moisture absorption
Rate, low dielectric constant and good processing characteristics, solubility property and adhesion property.
Brief description of the drawings
Fig. 1 is C-C bridgings [ONNO] of the present invention-acetylacetone,2,4-pentanedione fluorenes imine nickel (II) mono-crystalline structures figure.
Fig. 2 is C-C bridgings [ONNO] of the present invention-trifluoroacetylacetone (TFA) fluorenes imine nickel (II) mono-crystalline structures figure.
Embodiment
The present invention will be described further by following examples.
Embodiment 1.
(I) preparation of acetylacetone,2,4-pentanedione fluorenes imine ligand.
The anhydrous of 9- amino fluorene hydrochlorate (5.44g, 0.025mol) and 100ml is sequentially added in 250ml branch mouthful bottle
Ethanol solution, stirring adds triethylamine (2.54g, 0.025mol) untill dissolving, at room temperature and stirs standing after 2 hours
Half an hour.Supernatant is transferred in the ethanol solution equipped with acetylacetone,2,4-pentanedione (2.50g, 0.025mol), adds 0.8mL's
Glacial acetic acid is heated to reflux 24 hours, is under vacuo taken away remaining solvent with cold-trap, the solid of precipitation silicagel column with just oneself
Alkane/ethyl acetate (50:1) purified, after purification, separated out in the mixed solvent of n-hexane and ethyl acetate as eluant, eluent
Yellow crystals, purity reaches 98%.
(II) synthesis of C-C bridgings [ONNO]-acetylacetone,2,4-pentanedione fluorenes imine nickel (II) catalyst.
Part (0.53g, 0.002mol) prepared by step I is added in the 100mL branch equipped with magnetic stir bar mouthful bottles,
The dried THF of 40mL are added under nitrogen protective condition, stirring is completely dissolved part.By NaH (0.144g, 0.006mol)
It is added under nitrogen protection in mixed liquor, solution colour is changed into yellow green.It is small that 4 are stirred vigorously under nitrogen atmosphere and normal temperature
When, then THF is all removed with cold-trap, the mixed-powder of grey is obtained.Under nitrogen protection, added into mixture at 15mL
The dichloromethane solution managed, then adds glycol dimethyl ether nickelous bromide, after stirring 8 hours at room temperature, is entered with core filter bulb
Row filtering, collects filtrate, and is recrystallized, and obtains bridging [ONNO]-acetylacetone,2,4-pentanedione fluorenes imine nickel (II) complex crystal.1H
NMR(CDCl3,δ,ppm):1.92(s,6H,CH3),2.23(s,6H,CH3), 4.59 (s, 2H, CH), 7.11-7.89 (m, 16H,
C13H8).13C NMR(CDCl3,δ,ppm):17.21,25.23,64.40,127.61,131.23,134.32,140.36,
143.68,147.82,150.73,169.54.Anal.Calc.for C36H30O2N2Ni:C,74.38；H,5.20；N,
4.82.Found:C,74.40；H,5.19；N,4.79.
(III) application in ENB homopolymerization preparation.
The reaction bulb equipped with magnetic stir bar and with branch mouthful is heated with heat gun, while being vacuumized to it, nitrogen charging
Gas disposal, is replaced three times, it is ensured that reaction system is in dry nitrogen environment.5-8mL is injected into bottle by syringe successively
Toluene, 1.2-2.4mL ENB toluene solution (ρ=0.4g/mL), 1mL B (C6F5)3Toluene solution (M=
0.01-10Mol/L), the toluene solution of 1mL major catalyst C-C bridgings [ONNO]-acetylacetone,2,4-pentanedione fluorenes imine nickel (II) complex,
Reacted at 60 DEG C 30 minutes, then major catalyst and co-catalyst are decomposed with 100mL 10% ethanol solution hydrochloride, terminated
Reaction, stands 12 hours, polymer is settled complete.Will precipitation filtering and at 40 DEG C in vacuum drying chamber dry 24 hours with
Up to constant weight.Wherein the conversion ratio of polymer is 75-100%, and catalytic activity is 1.02 × 106gpolymer/molNi·h。
Embodiment 2.
(I) preparation of trifluoroacetylacetone (TFA) fluorenamine part.
The anhydrous of 9- amino fluorene hydrochlorate (5.44g, 0.025mol) and 100ml is sequentially added in 250ml branch mouthful bottle
Ethanol solution, stirring adds triethylamine (2.54g, 0.025mol) untill dissolving, at room temperature and stirs standing after 2 hours
Half an hour.Supernatant is transferred in the ethanol solution equipped with trifluoroacetylacetone (TFA) (4.25g, 0.025mol), added
0.8mL glacial acetic acid is heated to reflux 24 hours.Remaining solvent is taken away with cold-trap device under vacuo, the solid of precipitation is in silicon
Glue post n-hexane/ethyl acetate (50:1) purified as eluant, eluent, after purification, in the mixing of n-hexane and ethyl acetate
Yellow crystals are separated out in solvent, purity reaches 99%.
(II) synthesis of C-C bridgings [ONNO]-trifluoroacetylacetone (TFA) fluorenes imine nickel (II) catalyst.
Part (0.67g, 0.002mol) prepared by step I is added in the 100mL branch equipped with magnetic stir bar mouthful bottles,
The THF that 40mL is dried is added under nitrogen protective condition, stirring is completely dissolved part.NaH (0.144g, 0.004mol) is existed
It is added under nitrogen protection in mixed liquor, solution colour is changed into yellow green.It is stirred vigorously under nitrogen atmosphere and normal temperature 4 hours,
Then THF is all removed with cold-trap, obtains the mixed-powder of white and grey.Under nitrogen protection, added into mixture
The dichloromethane solution that 15mL is handled well, then adds glycol dimethyl ether nickelous bromide, after stirring 8 hours at room temperature, uses core
Filter bulb is filtered, and collects filtrate, and is recrystallized, and obtains C-C bridgings [ONNO]-trifluoroacetylacetone (TFA) fluorenes imine nickel (II)
Complex green crystal.1H NMR(CDCl3,δ,ppm):1.36(s,6H,CH3),5.33(s,2H,CH),7.09-7.16(m,
16H,C13H8).13C NMR(CDCl3,δ,ppm):20.36,74.40,125.89,127.65,128.63,130.41,131.62,
135.40,136.68,140.82,148.62,159.66,170.54.Anal.Calc.for C36H24O2F6N2Ni:C,62.73；
H,3.51；N,4.06.Found:C,62.75；H,3.48；N,4.09.
(III) application in ENB homopolymerization preparation.
The reaction bulb equipped with magnetic stir bar and with branch mouthful is heated with heat gun, while being vacuumized to it, nitrogen charging
Gas disposal, is replaced three times, it is ensured that reaction system is in dry nitrogen environment.5-8mL is injected into bottle by syringe successively
Toluene, 1.2-2.4mL ENB toluene solution (ρ=0.4g/mL), 1mL B (C6F5)3Toluene solution (M=
0.01-10Mol/L), 1mL major catalyst C-C bridgings [ONNO]-trifluoroacetylacetone (TFA) fluorenes imine nickel (II) complex toluene is molten
Liquid, reacts 30 minutes at 60 DEG C, is then decomposed major catalyst and co-catalyst with 100mL 10% ethanol solution hydrochloride,
Terminating reaction, stands 12 hours, polymer is settled complete.Filtering will be precipitated and drying 24 will be small in vacuum drying chamber at 40 DEG C
When with up to constant weight.Wherein the conversion ratio of polymer is 80-100%, and catalytic activity is 1.2 × 106gpolymer/molNi·h。
Embodiment 3.
(I) preparation of acetylacetone,2,4-pentanedione NSC 334072 part.
Sequentially added in 250ml branch mouthful bottle benzhydrylamine (4.58g, 0.025mol), acetylacetone,2,4-pentanedione (2.50g,
0.025mol) with 150mL ethanol, the glacial acetic acid for adding 0.8mL is heated to reflux 24 hours, under vacuo will be remaining with cold-trap
Solvent is taken away, and the solid of precipitation is in silicagel column n-hexane/ethyl acetate (100:1) purified as eluant, eluent, after purification,
White crystal is separated out in the mixed solvent of n-hexane and ethyl acetate, purity reaches 99%.
(II) synthesis of C-C bridgings [ONNO]-acetylacetone,2,4-pentanedione NSC 334072 palladium (II) catalyst.
Part (0.53g, 0.002mol) prepared by step I is added in the 100mL branch equipped with magnetic stir bar mouthful bottles,
The dried THF of 40mL are added under nitrogen protective condition, stirring is completely dissolved part.By NaH (0.144g, 0.006mol)
It is added under nitrogen protection in mixed liquor, solution colour is changed into brown color.It is small that 4 are stirred vigorously under nitrogen atmosphere and normal temperature
When, then THF is all removed with cold-trap, linen mixed-powder is obtained.Under nitrogen protection, 15mL is added into mixture
The toluene solution handled well, then adds tetraethyl amine tetrachloro and closes sour palladium, after stirring 8 hours at room temperature, carried out with core filter bulb
Filtering, collects filtrate, and is recrystallized, and obtains bridging [ONNO]-acetylacetone,2,4-pentanedione NSC 334072 palladium (II) complex reddish brown
Color crystal.1H NMR(CDCl3,δ,ppm):1.34(s,6H,CH3),1.78(s,6H,CH3), 4.12 (s, 2H, CH), 4.65 (s,
2H,CH),7.12-7.33(m,20H,C6H5).13C NMR(CDCl3,δ,ppm):23.33,26.21,48.23,70.02,
102.73,126.08,128.49,129.02,143.01,145.55.Anal.Calc.for C36H36O2N2Pd:C,68.08；H,
5.71；N,4.41.Found:C,68.10；H,5.67；N,4.42.
(III) application in ENB homopolymerization preparation.
The reaction bulb equipped with magnetic stir bar and with branch mouthful is heated with heat gun, while being vacuumized to it, nitrogen charging
Gas disposal, is replaced three times, it is ensured that reaction system is in dry nitrogen environment.5-8mL is injected into bottle by syringe successively
Toluene, 1.2-2.4mL ENB toluene solution (ρ=0.4g/mL), 1mL B (C6F5)3Toluene solution (M=
0.01-10mol/L), the toluene of 1mL major catalyst C-C bridgings [ONNO]-acetylacetone,2,4-pentanedione NSC 334072 palladium (II) complex
Solution, reacts 30 minutes at 60 DEG C, is then divided major catalyst and co-catalyst with 100mL 10% ethanol solution hydrochloride
Solution, terminating reaction stands 12 hours, polymer is settled complete.Dried by precipitation filtering and at 40 DEG C in vacuum drying chamber
24 hours with up to constant weight.Wherein the conversion ratio of polymer is 90-100%, and catalytic activity is 0.97 × 106gpolymer/
molNi·h。
Embodiment 4.
(I) preparation of 1- benzoyl acetones benzyl imine ligand.
Sequentially added in 250ml branch mouthful bottle benzylamine (2.7g, 0.025mol), 1- benzoyl acetones (4.05g,
0.025mol) with 150mL ethanol, the glacial acetic acid for adding 0.8mL is heated to reflux 24 hours, under vacuo will be remaining with cold-trap
Solvent is taken away, and the solid of precipitation is in silicagel column n-hexane/ethyl acetate (30:1) purified as eluant, eluent, after purification,
Yellow crystals are separated out in the mixed solvent of n-hexane and ethyl acetate, purity reaches 95%.
(II) synthesis of C-C bridgings [ONNO] -1- benzoyl acetone benzyl imines cobalt (II) catalyst.
Part (0.502g, 0.002mol) prepared by step I is added to the 100mL branch equipped with magnetic stir bar mouthful bottles
In, the dried THF of 40mL are added under nitrogen protective condition, stirring is completely dissolved part.By NaH (0.144g,
0.006mol) it is added under nitrogen protection in mixed liquor, solution colour is changed into brown color.Under nitrogen atmosphere and normal temperature acutely
Stirring 6 hours, then THF is all removed, obtain buff powder with cold-trap.Under nitrogen protection, added into mixture
The toluene solution that 15mL is handled well, then adds cobalt chloride, after stirring 8 hours at room temperature, is filtered with core filter bulb, collects
Filtrate, and recrystallized, obtain bridging [ONNO] -1- benzoyl acetone benzyl imines cobalt (II) complex peony crystal.1H
NMR(CDCl3,δ,ppm):1.74(s,6H,CH3), 4.52 (s, 2H, CH), 4.89 (s, 2H, CH), 5.17 (s, 2H, CH),
7.09-7.24(m,20H,C6H5).13C NMR(CDCl3,δ,ppm):26.17,50.35,55.74,102.72,126.38,
127.47,128.82,140.56,142.33,145.71.Anal.Calc.for C34H32O2N2Co:C,72.98；H,5.76；N,
5.01.Found:C,72.79；H,5.84；N,4.92.
(III) application in ENB homopolymerization preparation.
The reaction bulb equipped with magnetic stir bar and with branch mouthful is heated with heat gun, while being vacuumized to it, nitrogen charging
Gas disposal, is replaced three times, it is ensured that reaction system is in dry nitrogen environment.5-8mL is injected into bottle by syringe successively
Toluene, 1.2-2.4mL ENB toluene solution (ρ=0.4g/mL), 1mL B (C6F5)3Toluene solution (M=
0.01-10mol/L), the toluene of 1mL major catalyst C-C bridgings [ONNO] -1- benzoyl acetone benzyl imines cobalt (II) complex
Solution, reacts 30 minutes at 60 DEG C, is then divided major catalyst and co-catalyst with 100mL 10% ethanol solution hydrochloride
Solution, terminating reaction stands 12 hours, polymer is settled complete.Dried by precipitation filtering and at 40 DEG C in vacuum drying chamber
24 hours with up to constant weight.Wherein the conversion ratio of polymer is 80-100%, and catalytic activity is 9.4 × 104gpolymer/molNi·
h。
Claims (2)
1. a kind of C-C bridgings [ONNO]-beta-ketimine gold for ENB and the addition copolymerization of norbornene derivative
Metal catalyst, its general structure is：
Wherein, M=Ni, Pd, Co, Fe or Cu；
R1、R2、R3For：
(1)R1=CH3, R2=CH3,
(2)R1=CH3, R2=CF3,
(3)R1=CH3,
(4)R1=CH3, R2=CH3,
(5)R1=CH3, R2=CF3,
(6)R1=CH3,
(7)R1=CH3, R2=CH3,
(8)R1=CH3, R2=CF3,
(9)R1=CH3,
(10)R1=CH2CH(CH3)2, R2=CH3,
(11)R1=CH2CH(CH3)2, R2=CH3,
(12)R1=CH2CH(CH3)2, R2=CH3,
(13)R1=CF3, R2=CF3,
(14)R1=CF3,
(15)R1=CF3, R2=CF3,
(16)R1=CF3,
(17)R1=CF3, R2=CF3,
(18)R1=CF3,
(19)
(20)
(21)
2. the preparation method of C-C bridgings [ONNO]-beta-ketimine metallic catalyst described in claim 1, it is characterized in that including
Following steps：
(I) it is 1 that mol ratio is added in the reaction bulb equipped with reflux condensing tube and water knockout drum:1 beta-diketon and the fragrance of-H containing α
Amine, and catalytic amount glacial acetic acid and 50-300mL ethanol, reaction 8-48 hour after, with n-hexane recrystallize or vacuum distillation
Obtain beta-ketimine part；
(II) NaH is added in the tetrahydrofuran solution containing beta-ketimine part under nitrogen atmosphere, NaH matches somebody with somebody with beta-ketimine
The molar ratio of body is 1:2,4-8h is stirred at room temperature, and the pre- part of trans metal of 1/2 equivalent is added afterwards, is persistently stirred at room temperature
8-12h is mixed, filters, is recrystallized to give C-C bridgings [ONNO]-beta-ketimine metal complex.
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