CN103102433B - Alpha-diimine palladium (II) olefin polymerization catalyst containing substituted ortho-phenyls, as well as preparation and application thereof - Google Patents
Alpha-diimine palladium (II) olefin polymerization catalyst containing substituted ortho-phenyls, as well as preparation and application thereof Download PDFInfo
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- CN103102433B CN103102433B CN201310010493.2A CN201310010493A CN103102433B CN 103102433 B CN103102433 B CN 103102433B CN 201310010493 A CN201310010493 A CN 201310010493A CN 103102433 B CN103102433 B CN 103102433B
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Abstract
The invention discloses a novel post-transition metal alpha-diimine palladium (II) olefin polymerization catalyst containing substituted ortho-phenyls, wherein two large-volume groups, namely phenyls are introduced in ortho positions of an aromatic ring of nitrogen atoms of imine. As the phenyls have the larger volume, the metal center of the catalyst can be effectively protected, the instability in basic-state activity is increased, the insertion process of ethylene monomers is accelerated and the high activity of the catalyst is further improved. Simultaneously, the space effect of a large-volume ligand can greatly reduce the transfer rate of an active chain to the monomers, so that a high molecular weight polymer can be obtained. In the presence of a cocatalyst, namely diethylaluminum chloride (DEAC), the catalyst has higher catalytic activity (which can achieve 106gPE/(mol Pd.h.Bar)) in catalysis of ethylene polymerization, and obtained polyethylene has higher degree of branching (which can achieve 123 branched chains/1000C). Therefore, the catalyst has great application value in olefin polymerization industry.
Description
Technical field
The invention belongs to technical field of macromolecules, relate to a class olefin polymerization catalysis, relate in particular to a class and contain rear transition metal alpha-diimine palladium (II) olefin polymerization catalysis that ortho position phenyl replaces; Invention also relates to the preparation method of this catalyzer and the application in vinyl polymerization thereof simultaneously.
Background technology
Polyolefine is the synthetic resins of consumption maximum, has improved to a great extent daily life.And the discovery of high activity olefin polymerization catalyst has played critical effect to synthetic new polymkeric substance.Found the Ni(II containing alpha-diimine part from Brookhart etc.) with Pd(II) since title complex can make the alpha-olefine polymerizing become the polymkeric substance of high molecular, late transition metal catalyst has caused that scientists pays close attention to widely.Due to a little less than a notable feature of late transition metal catalyst is central metal atom Electron Affinities, resistance to heteroatomic ability is strong, so such catalyzer not only can be for the polymerization in homogeneous phase of ethene, also can be used for the copolymerization of alkene and polar monomer, thereby produce the Functional Polyolefins of excellent performance.For alpha-diimine type catalyzer, Johnson etc. think and on aniline, introduce large substituting group, its steric effect and they are very crucial to the spatial positioning on the actual summit of square planar complex to the polyreaction of monomer, in the time of catalyzed ethylene polymerization, can show higher catalytic activity, therefore, design has been synthesized a class and has been contained alpha-diimine palladium (II) ethylene polymerization catalyzed system that phenyl large steric hindrance in ortho position replaces, and be applied to vinyl polymerization, wish to utilize substituent sterically hindered chain walking while suppressing polymerization, to obtain the polyolefine that regularity is higher.
Summary of the invention
The object of the present invention is to provide a class to contain alpha-diimine palladium (II) olefin polymerization catalysis that phenyl large steric hindrance in ortho position replaces.
Another order of the present invention is to be to provide the preparation method of above-mentioned alpha-diimine palladium (II) olefin polymerization catalysis that contains the large steric hindrance replacement of ortho position phenyl.
A further object of the present invention is to provide the application of the above-mentioned alpha-diimine palladium (II) that contains the large steric hindrance replacement of ortho position phenyl in vinyl polymerization.
(1) contain alpha-diimine palladium (II) olefin polymerization catalysis that ortho position phenyl replaces
Alpha-diimine palladium (II) olefin polymerization catalysis that contains the large steric hindrance replacement of ortho position phenyl of the present invention's design, its structure is as follows:
Wherein, R
1for halogen, C1 ~ C4 alkyl; R
2for halogen, hydrogen.
Alpha-diimine nickel of the present invention (II) title complex is to introduce two bulky group phenyl at the ortho position of imine nitrogen atom aromatic ring.Because phenyl has comparatively large vol, guard catalyst metal center effectively, has increased the unstable in ground state activity, has accelerated the process that vinyl monomer inserts, thereby has improved the high reactivity of catalyzer.Meanwhile, the steric effect of bulky ligand has reduced the transfer rate of living chain to monomer greatly, thereby obtains high-molecular weight polymer.
(2) preparation of alpha-diimine palladium (II) olefin polymerization catalysis that contains ortho position phenyl replacement
The preparation method of alpha-diimine palladium (II) olefin polymerization catalysis that contains ortho position phenyl replacement the present invention relates to, comprises following processing step:
(1) preparation of the aniline category matter that ortho position bromine replaces: taking methylene dichloride as solvent, aniline at room temperature reacts 20 ~ 30min with glacial acetic acid with the mol ratio of 1:1.5 ~ 1:6, obtains phenyl acetanilide,Phenacetylaniline class material; Add again the bromine (bromine is dissolved in and is slowly added dropwise to reaction system in methylene dichloride) of aniline molar weight 1:2.0 ~ 2.2 times, stirring reaction 3 ~ 5h at 0 ~ 5 DEG C; After reacting completely, except desolventizing, neutralize with strong base solution, use again petroleum ether extraction organic phase, anhydrous magnesium sulfate drying, filtering and concentrating, column chromatography for separation (eluent is to be mixed with the volume ratio of 1:5 ~ 1:15 with sherwood oil by ethyl acetate), obtains the aniline category matter that ortho position bromine replaces.
(2) preparation of the aniline category matter that ortho position phenyl replaces: taking PEG-400 as solvent, taking Palladous chloride as catalyzer, the aniline category matter that phenylo boric acid and ortho position bromine replace, with the mixed in molar ratio of 1:2.0 ~ 1:2.2, is adjusted pH=7 ~ 11 of system, stirring reaction 12 ~ 24 hours; After reacting completely, by extracted with diethyl ether, anhydrous magnesium sulfate drying, filters, concentrated, and silica gel column chromatography separates (eluent is to be mixed with the volume ratio of 1:15 ~ 1:30 with sherwood oil by ethyl acetate), obtains the aniline category matter that ortho position phenyl replaces.
The aniline category matter that described ortho position bromine replaces is that 4-is fluoro-2,6-dibromo aniline, and 4-is chloro-2,6-dibromo aniline, the fluoro-3-of 4-is chloro-2,6-dibromo aniline, 4-methyl-2,6-dibromo aniline, 4-normal-butyl-2,6-dibromo aniline.
The consumption of described catalyzer Palladous chloride is 0.5 ~ 4% of phenylo boric acid molar weight.
(3) preparation of the part with symmetrical schiff bases structure that contains ortho position phenyl replacement: taking benzene as solvent, taking p-methyl benzenesulfonic acid as catalyzer, the aniline category matter that ortho position phenyl is replaced and acenaphthenequinone are with the mixed in molar ratio of 2.0:1 ~ 2.2:1, at 80 ~ 90 DEG C, back flow reaction is after 12 ~ 48 hours, except desolventizing, silica gel column chromatography separates (eluent that silica gel column chromatography separates is to be mixed with the volume ratio of 1:10 ~ 1:25 with sherwood oil by ethyl acetate), and vacuum-drying obtains part.
The consumption of described catalyzer p-methyl benzenesulfonic acid is 2 ~ 10% of acenaphthenequinone molar weight.
(4) preparation of alpha-diimine palladium (II) olefin polymerization catalysis that contains the large steric hindrance replacement of ortho position phenyl: under nitrogen protection; taking methylene dichloride as solvent; ortho position the phenyl part with symmetrical schiff bases structure replacing and the Palladous chloride being activated by the acetonitrile mixed in molar ratio with 1:1 ~ 1:1.2 will be contained; at room temperature stirring reaction is after 12 ~ 24 hours; filtering suspension liquid, mother liquor except after desolventizing, washs with ether under vacuum condition; vacuum-drying, obtains pulverulent solids title complex.
Described Palladous chloride (the PdCl being activated by acetonitrile
2(MeCN)
2) preparation method be: the mixed in molar ratio by Palladous chloride and acetonitrile with 1:8 ~ 1:50, the 5 ~ 10h that refluxes at 60 ~ 70 DEG C, filters, concentrated, vacuum-drying, obtains pulverulent solids PdCl
2(MeCN)
2.
Above-mentioned synthesis type is as follows:
Product prepared by aforesaid method adopts U.S. Mercury-400 plus nuclear magnetic resonance analyser through NMR (Nuclear Magnetic Resonance) spectrum (NMR); Infrared spectra (FTIR) adopts U.S. Digilab Merlin FTS 3000 FT-IR infrared spectrometers; The APEX CCD of Bruker company II type X-single crystal diffractometer; Ultimate analysis adopts the mensuration of the instruments such as Vario.EL type elemental analyser, proves that synthetic product is consistent with the compound structure of design.
(3) contain the application of alpha-diimine palladium (II) olefin polymerization catalysis in vinyl polymerization that ortho position phenyl replaces
Alpha-diimine palladium (II) ethylene rolymerization catalyst the present invention relates to; because making the cloud density at catalyst metal center and metal center space steric effect around, the existence of ortho position phenyl changes (at two large steric group phenyl of the ortho position of imine nitrogen atom aromatic ring introducing; guard catalyst metal center electron density effectively); and then make this catalyzer under the existence of promotor diethylaluminum chloride; catalyzed ethylene polymerization has higher activity, and the polymkeric substance of gained has the higher degree of branching.
Experimental results demonstrate, in ethylene polymerization, temperature of reaction is controlled at 0 ~ 60 DEG C, and the reaction times is 5 ~ 20 minutes, and the consumption of catalyzer is
time, this catalyst system catalyzed ethylene polymerization has higher catalytic activity (can reach 10
6gPE/ (mol Pd
h
bar), bibliographical information is containing alpha-diimine palladium (II) the catalyst activity 10 of 2，4，6-trimethyl aniline
5gPE/ (mol Pd
h
bar), so alpha-diimine palladium (II) catalyzer of the existence of ortho position phenyl has potential industrial value), and the polyethylene obtaining has the higher degree of branching (can reach 123 side chain/1000C).
Brief description of the drawings
Fig. 1 is the single crystal diffraction figure of the ethylene rolymerization catalyst of the preparation of the embodiment of the present invention 1.
Embodiment
The preparation of alpha-diimine palladium (II) olefin polymerization catalysis that the present invention is contained to ortho position phenyl replacement below by specific embodiment and the application in vinyl polymerization are described further.
The raw material using in embodiment and reagent: all metal organic reactions are all at N
2under protection, carry out, the equal drying deoxygenation of solvent processing, methylene dichloride and orthodichlorobenzene (analytical pure), with 4
after molecular sieve is predrying at N
2under atmosphere through CaH
2reflux, before use, steam.Toluene, ether (analytical pure) add sodium Metal 99.5 to reflux after molecular sieve dehydration under nitrogen protection, before use, steam.High-purity N
2before using with polymer grade ethylene monomer, deoxygenation is dry.Anhydrous methanol, ethanol, trichloromethane (analytical pure), directly use.DME (1,2-glycol dimethyl ether) (analytical pure), with 4
molecular sieve drying.Acenaphthenequinone, 4-monomethylaniline, 4-chloroaniline, 4-n-butyl aniline, 4-fluoroaniline, the chloro-4-fluoroaniline of 3-, bromine, Palladous chloride, diethylaluminum chloride (toluene solution of 0.9M), be Aldrich company product, and phenylo boric acid is Bei Jinghui Yan Rui section product.PdCl
2(MeCN)
2prepare and obtain by following methods: the mixed in molar ratio by Palladous chloride and acetonitrile with 1:8 ~ 1:50, the 5 ~ 10h that refluxes at 60 ~ 70 DEG C, filters, and concentrated, vacuum-drying, obtains pulverulent solids PdCl
2(MeCN)
2.
Embodiment 1
(1) 4-is fluoro-2,6-dibromo aniline synthetic: take para-fluoroaniline (5.0mmol, 0.56g), add the methylene dichloride of 30ml, low-grade fever is dissolved it completely, then adds glacial acetic acid (2mL), under room temperature, reacts 30min; System is placed in to ice bath, in system, slowly splashes into bromine (10.5mmol, 1.68g), stirring reaction 3h.After question response finishes, slowly add saturated aqueous sodium hydroxide solution neutralization, then use petroleum ether extraction organic phase (25mL × 3), anhydrous magnesium sulfate drying, filtering and concentrating, with silica gel column chromatography (ethyl acetate: sherwood oil=1:7(v/v)) separate, concentrate to obtain gray solid 1.14g.Productive rate 85%.
1H NMR (400MHz, CDCl
3): δ 4.63 (s, 2H, -N
H 2), 7.08 (s, 2H, C
6 H 2-NH
2).
13C NMR (400 MHz, CDCl
3): δ 120.48 (
C 6H
2-NH
2), 121.15 (
C 6H
2-NH
2), 149.12 (
C 6H
2-NH
2), 157.45 (
C 6H
2-NH
2)。
Its reaction formula is as follows:
(2) 4-fluoro-2, synthesizing of 6-phenylbenzene aniline: successively by palladium (0.04mmol, 0.01g), phenylo boric acid (4.4mmol, 0.54g), 4-fluoro-2, 6-dibromo aniline (2.0mmol, 0.54g) and salt of wormwood (4.0mmol, 0.55g) join in the PEG-4000 solvent of 10mL, add again the water of 0.5ml, at room temperature stirring reaction 24 hours, after reaction, use extracted with diethyl ether, extraction liquid anhydrous magnesium sulfate drying, filter, after concentrated, adopt silica gel column chromatography (ethyl acetate: sherwood oil=1:10(v/v)) separate, obtain 4-fluoro-2, 6-phenylbenzene aniline 0.35g.Productive rate is 66%.
1H NMR (400MHz, CDCl
3): δ 3.66 (s, 2H, -N
H 2), 6.86 (d,
J=7.6 HZ, 2H, C
6 H 2-NH
2), 7.36 (t,
J=7.2 HZ, 2H, C
6 H 5-), 7.43-7.49 (m, 8H, C
6 H 5-).
13C NMR (400 MHz, CDCl
3): δ 115.81 (
C 6H
2-NH
2), 127.63 (
C 6H
2-NH
2), 128.83 (
C 6H
5-), 128.92 (
C 6H
5-), 129.12 (
C 6H
5-), 136.90 (
C 6H
5-), 138.80 (
C 6H
2-NH
2), 154.63 (
C 6H
2-NH
2)。
Its reaction formula is as follows:
(3) part (4-F-2,6-diPhPh)
2dABAn's is synthetic: by fluoro-4-2,6-phenylbenzene aniline (2.2mmol, 0.58g) and acenaphthenequinone (1.0mmol, 0.18g) be dissolved in 20mL benzene, under agitation add p-methyl benzenesulfonic acid (0.1mmol, 20mg), at 88 DEG C, back flow reaction is after 24 hours, and except desolventizing, thick product separates (ethyl acetate: sherwood oil=1:20(v/v) with silica gel column chromatography), vacuum-drying, obtains safran pulverulent solids 0.45g.Productive rate is 67%.
1H NMR (400 MHz, CDCl
3): δ 6.77 (t,
J=7.2 HZ, 2H,Nap-
H), 6.93 (t,
J=7.6 HZ, 4H, C
6 H 5-), 7.05 (d,
J=6.8 HZ, 4H,Nap-
H), 7.10 (t,
J=7.6 HZ, 8H, C
6 H 5-), 7.27 (t,
J=7.2 HZ, 8H, C
6 H 5-), 7.29 (d,
J=7.2 HZ, 4H, C
6 H 2-F), 7.67 (d,
J=8.4 HZ, 2H, Nap-
H).
13C NMR (400 MHz, CDCl
3): δ 116.81 (Nap-
C), 122.53 (Nap-
C), 127.01 (
C 6H
2-F), 127.11 (
C 6H
5-), 128.10 (
C 6H
5-), 129.01 (
C 6H
5-), 129.69 (
C 6H
2-F), 130.37 (
C 6H
5-), 133.27 (Nap-
C), 138.78 (Nap-
C), 140.05 (Nap-
C), 142.99 (Nap-
C), 158.51 (
C 6H
2-F), 161.13 (
C=N), 161.77 (
C 6H
2-F). Anal. Calc. for C
48H
30F
2N
2: C, 85.69; H, 4.49; N, 4.16. Found: C, 85.66; H, 4.52; N, 4.18。
Its reaction formula is as follows:
(4) title complex PdCl
2(4-F-2,6-diPhPh)
2dABAn's is synthetic: under nitrogen protection, add above-mentioned part (0.5mmol, 0.33g), then add PdCl in the dry reaction tubes of 100mL
2(MeCN)
2(0.5mmol, 0.13g) and methylene dichloride 30mL, at room temperature stirring reaction 16 hours, filtering suspension liquid, mother liquor is except desolventizing under vacuum, and ether for residue (3 × 16mL) washing three times, obtains gray powder powder solid complexes 0.35g after vacuum-drying.Productive rate is 88%.
Anal. Calcd. for C
48H
30Br
2F
2 N
2Ni: C, 64.68; H, 3.39; N, 3.14. Found: C, 64.64; H, 3.43; N, 3.17。
Its reaction formula is as follows:
(5) vinyl polymerization: by the 250mL polymerization bottle vacuum with magnetic stick-nitrogen circulation displacement three times, under nitrogen atmosphere, add 50mL toluene solution, pass into again ethene, ethene is fully absorbed until saturated, then with being with graduated syringe by promotor diethylaluminum chloride (DEAC) (3.3mL, 0.9M, n (Al)/n (Pd)=600) add in reaction flask, design temperature is 20 DEG C and maintains reaction stirring after 15 minutes, add the o-dichlorobenzene solution that has dissolved nickel catalyzator (2.24mmol) through syringe, regulate ethene intake to make the pressure of polymerization system maintain 0.02MPa.At 20 DEG C, ethylene polymerization was carried out after 10 minutes, add 5% acidifying methyl alcohol termination reaction, then add the vibration of 100mL methyl alcohol, be settled out polymerisate.Precipitation leaves standstill after 24 hours and filters, and fully washs with anhydrous methanol, and 50 DEG C of vacuum-drying 48 hours, obtains polyethylene 2.22g, and activity is 4.95 × 10
6g PE/(mol Pd
h
bar).
(6) polymerisate is analyzed through differential thermal analysis (DSC) and gel permeation chromatography (GPC), at 60 DEG C, and fusing point (T
m) be 96 DEG C, weight-average molecular weight is 5.5 × 10
4, number-average molecular weight is 1.07 × 10
5, molecular weight distribution 1.95, the degree of branching is 123 side chain/1000C.
Embodiment 2
(1) 4-is chloro-2,6-dibromo aniline synthetic: take p-Chlorobenzoic acid amide (5.0mmol, 0.64g), add the methylene dichloride of 30ml, low-grade fever is dissolved it completely, then adds glacial acetic acid (2mL), under room temperature, reacts 20min; System is placed in to ice bath, in system, slowly splashes into bromine (12.5mmol, 2.00g), stirring reaction 5h.After question response finishes, slowly add saturated aqueous sodium hydroxide solution neutralization, then use petroleum ether extraction organic phase (30mL × 3), anhydrous magnesium sulfate drying, filtering and concentrating, with silica gel column chromatography (ethyl acetate: sherwood oil=1:15(v/v)) separate, concentrate to obtain white solid 1.75g.Productive rate 66%.
1H NMR (400MHz, CDCl
3): δ 4.55 (s, 2H, -N
H 2), 7.38 (s, 2H, C
6 H 2-NH
2).
13C NMR (400 MHz, CDCl
3): δ 108.43 (
C 6H
2-NH
2), 130.48 (
C 6H
2-NH
2), 131.46 (
C 6H
2-NH
2), 141.25 (
C 6H
2-NH
2).
Its reaction formula is as follows:
(2) 4-chloro-2, synthesizing of 6-phenylbenzene aniline: successively by palladium (0.04mmol, 0.01g), phenylo boric acid (4.4mmol, 0.54g), 4-chloro-2, 6-dibromo aniline (2mmol, 0.57g) and salt of wormwood (4.0mmol, 0.55g) join in the PEG-4000 solvent of 25mL, add again the water of 0.5ml, at room temperature stirring reaction 36 hours, after reaction, use extracted with diethyl ether, extraction liquid anhydrous magnesium sulfate drying, filter, after concentrated, adopt silica gel column chromatography to separate (ethyl acetate: sherwood oil=1:25(v/v)), obtain 4-chloro-2, 6-phenylbenzene aniline 0.34g.Productive rate is 60%.
1H NMR (400MHz, CDCl
3): δ 3.71 (s, 2H, -N
H 2), 7.00 (s, 2H, C
6 H 2-NH
2), 7.25-7.30 (m, 2H, C
6 H 5-), 7.33-7.40 (m, 8H, C
6 H 5-).
13C NMR (400 MHz, CDCl
3): δ 124.82 (
C 6H
2-NH
2), 127.47 (
C 6H
2-NH
2), 128.38 (
C 6H
2-NH
2), 128.98 (
C 6H
5-), 129.58 (
C 6H
5-), 130.46 (
C 6H
5-), 138.46 (
C 6H
5-), 139.74 (
C 6H
2-NH
2)。
Its reaction formula is as follows:
(3) part (4-Cl-2,6-diPhPh)
2dABAn's is synthetic: by chloro-4-2,6-phenylbenzene aniline (2.2mmol, 0.62g) and acenaphthenequinone (1.0mmol, 0.18g) be dissolved in 20mL benzene, under agitation add p-methyl benzenesulfonic acid (0.1mmol, 20mg), at 88 DEG C, back flow reaction is after 48 hours, except desolventizing, by this thick silica gel column chromatography (ethyl acetate: sherwood oil=1:15(v/v) product for) separation, vacuum-drying, obtains safran pulverulent solids 0.46g.Productive rate is 65%.
1H NMR (400 MHz, CDCl
3): δ 6.83 (t,
J=7.6 HZ, 2H,Nap-
H), 6.92 (t,
J=7.6 HZ, 8H, C
6 H 5-), 7.05 (t,
J=7.6 HZ, 4H, C
6 H 5-), 7.26 (d,
J=7.6 HZ, 8H, C
6 H 5-), 7.30 (d,
J=7.6 HZ, 2H, Nap-
H), 7.34 (s, 4H, C
6 H 2-Cl), 7.70 (d,
J=8.4 HZ, 2H, Nap-
H).
13C NMR (400 MHz, CDCl
3): δ 122.66 (Nap-
C), 127.10 (Nap-
C), 127.40 (
C 6H
5-), 127.70 (
C 6H
2-Cl), 128.00 (
C 6H
5-), 129.06 (
C 6H
5-), 129.66 (
C 6H
2-Cl), 130.18 (
C 6H
5-), 130.64 (Nap-
C) 131.76 (Nap-
C), 132.82 (
C 6H
2-Cl), 137.78 (Nap-
C), 138.39 (Nap-
C), 139.36 (
C 6H
2-Cl), 160.36 (
C=N). Anal. Calcd. For C
48H
30Cl
2N
2: C, 81.70; H, 4.29; N, 3.97. Found: C, 81.73; H, 4.26; N, 3.95。
Its reaction formula is as follows:
(4) title complex PdCl
2(4-Cl-2,6-diPhPh)
2dABAn's is synthetic: under nitrogen protection, add above-mentioned part (0.5mmol, 0.34g), then add PdCl in the dry reaction tubes of 100mL
2(MeCN)
2(0.5mmol, 0.13g) and methylene dichloride 30mL, at room temperature reaction is stirred 16 hours, filtering suspension liquid, mother liquor is except desolventizing under vacuum, and ether for residue (3 × 16mL) washs three times, and vacuum-drying, obtains gray powder powder solid complexes 0.39g.Productive rate is 89%.
Anal. Calcd. For : C
48H
30Cl
4N
2Pd：C，65.29；H，3.42；N，3.17. Found：C，65.31；H，3.39；N，3.16。
Its reaction formula is as follows:
(5) vinyl polymerization: by the 250mL polymerization bottle vacuum with magnetic stick-nitrogen circulation displacement three times, under nitrogen atmosphere, add 50mL toluene solution, pass into again ethene, ethene is fully absorbed until saturated, then with being with graduated syringe by promotor diethylaluminum chloride (DEAC) (3.3mL, 0.9M, n (Al)/n (Pd)=600) add in reaction flask, design temperature is 10 DEG C and maintains reaction stirring after 15 minutes, add the o-dichlorobenzene solution that has dissolved nickel catalyzator (5 mmol) through syringe, regulate ethene intake to make the pressure of polymerization system maintain 0.02 MPa.At 20 DEG C, ethylene polymerization was carried out after 10 minutes, add 5% acidifying methyl alcohol termination reaction, then add 100 mL methyl alcohol vibrations, be settled out polymerisate.Precipitation leaves standstill after 24 hours and filters, and fully washs with anhydrous methanol, and 60 DEG C of vacuum-drying 48 hours, obtains polyethylene 1.2g, and activity is 1.02 × 10
6gPE/(molPd
h
bar).
(6) polymerisate is analyzed through differential thermal analysis (DSC) and gel permeation chromatography (GPC), and weight-average molecular weight is 1.89 × 10
5, number-average molecular weight is 1.21 × 10
5, molecular weight distribution 1.56, the degree of branching is 107 side chain/1000C.
Embodiment 3
(1) 4-methyl-2,6-dibromo aniline synthetic: take monomethylaniline (5.0mmol, 0.54g), add the methylene dichloride of 30ml, low-grade fever is dissolved it completely, then adds glacial acetic acid (2mL), reacts 30min under room temperature; System is placed in to ice bath, in system, slowly splashes into bromine (10.5mmol, 1.68g), stirring reaction 5h.After question response finishes, slowly add saturated aqueous sodium hydroxide solution neutralization, then use petroleum ether extraction organic phase (30mL × 3), anhydrous magnesium sulfate drying, filtering and concentrating, with silica gel column chromatography (ethyl acetate: sherwood oil=1:15(v/v)) separate, concentrate to obtain white solid 0.97 g.Productive rate 73%.
1H NMR (400MHz, CDCl
3): δ 2.20 (s, 3H, -C
H 3), 4.38 (s, 2H, -N
H 2), 7.19 (s, 2H, C
6 H 2-NH
2).
13C NMR (400 MHz, CDCl
3): δ 19.75 (C
6H
2-
CH
3), 108.69 (
C 6H
2-NH
2), 129.31 (
C 6H
2-NH
2), 132.13 (
C 6H
2-NH
2), 139.48 (
C 6H
2-NH
2)。
Its reaction formula is as follows:
(2) 4-methyl-2, synthesizing of 6-phenylbenzene aniline: successively by palladium (0.04mmol, 0.01g), phenylo boric acid (4.4mmol, 0.54g), 4-methyl-2, 6-dibromo aniline (2mmol, 0.53g) and salt of wormwood (4.0mmol, 0.55g) join in the PEG-4000 solvent of 20mL, add again the water of 0.5ml, at room temperature stirring reaction 20 hours, after reaction, use extracted with diethyl ether, extraction liquid anhydrous magnesium sulfate drying, filter, after concentrated, adopt silica gel column chromatography (ethyl acetate: sherwood oil=1:20(v/v)) separate, obtain 4-methyl-2, 6-phenylbenzene aniline 0.31g.Productive rate is 58%.
1H NMR (400MHz, CDCl
3): δ 2.21 (s, 3H,-C
H 3), 3.59 (s, 2H, -N
H 2), 6.78 (s, 2H, C
6 H 2-NH
2), 7.25 (t,
J=7.2 HZ, 2H, C
6 H 5-), 7.34 (t,
J=7.6 HZ, 4H, C
6 H 5-), 7.41 (d,
J=6.8 HZ, 4H, C
6 H 5-).
13C NMR (400 MHz, CDCl
3): δ 20.41 (-
CH
3), 127.15 (
C 6H
2-NH
2), 127.88 (C
6 H 5-), 128.69 (C
6 H 5-), 129.27 (C
6 H 5-), 129.42 (
C 6H
2-NH
2), 130.23 (
C 6H
2-NH
2), 138.13 (C
6 H 5-), 139.74 (
C 6H
2-NH
2)。
Its reaction formula is as follows:
(3) part (4-CH
3-2,6-diPhPh)
2dABAn's is synthetic: by 4-methyl-2,6-phenylbenzene aniline (2.2mmol, 0.57g) and acenaphthenequinone (1.0mmol, 0.18g) be dissolved in 20mL benzene, under agitation add p-methyl benzenesulfonic acid (0.1mmol, 20mg) to make catalyzer, at 88 DEG C, back flow reaction is after 24 ~ 48 hours, except desolventizing, this thick product is separated with silica gel column chromatography, vacuum-drying obtains safran pulverulent solids 0.41g.Productive rate is 62%.
1H NMR (400 MHz, CDCl
3): δ 2.37 (s, 6H, -C
H 3), 6.84 (t,
J=7.6 HZ, 8H, C
6 H 5-), 6.94 (t,
J=7.6 HZ, 4H, C
6 H 5-), 7.08 (s, 4H, C
6 H 2-CH
3), 7.21 (d,
J=7.6 HZ, 8H, C
6 H 5-), 7.42 (t,
J=7.6 HZ, 2H, Nap-
H), 7.43 (d,
J=7.2 HZ, 2H, Nap-
H), 7.55 (d,
J=8.4 HZ, 2H, Nap-
H).
13C NMR (400 MHz, CDCl
3): δ 20.32 (C
6H
2 -CH
3), 122.65 (Nap-
C), 126.42 (Nap-
C), 126.72 (
C 6H
5-), 127.25 (
C 6H
2 -CH
3), 127.85 (
C 6H
5-), 128.68 (
C 6H
5-), 129.68 (
C 6H
2 -CH
3), 130.41 (
C 6H
5-), 130.71 (Nap-
C), 131.69 (Nap-
C), 134.85 (Nap-
C), 137.93 (Nap-
C), 139.21 (
C 6H
2 -CH
3), 139.74 (
C 6H
2 -CH
3), 160.28 (C=N). Anal. Calcd. for C
50H
36N
2: C, 90.33; H, 5.46; N, 4.21. Found: C, 90.31; H, 5.49; N, 4.23。
Its reaction formula is as follows:
(4) title complex PdCl
2(4-CH
3-2,6-diPhPh)
2dABAn's is synthetic: under nitrogen protection, add above-mentioned part (0.5mmol, 0.41g), then add PdCl in the dry reaction tubes of 100mL
2(MeCN)
2(0.5mmol, 0.13g) and methylene dichloride 30mL, at room temperature stirring reaction 16 hours, filtering suspension liquid, mother liquor is except desolventizing under vacuum, and ether for residue (3 × 15mL) washing three times, obtains gray powder powder solid complexes 0.39g after vacuum-drying.Productive rate is 89%.
Anal. Calcd. For : C
50H
36Cl
2N
2Pd：C, 71.31; H, 4.31; N, 3.33. Found：C, 71.28; H, 4.33; N, 3.35。
Its reaction formula is as follows:
(5) vinyl polymerization: by the 250mL polymerization bottle vacuum with magnetic stick-nitrogen circulation displacement three times, under nitrogen atmosphere, add 50mL toluene solution, pass into again ethene, ethene is fully absorbed until saturated, then with being with graduated syringe by promotor diethylaluminum chloride (DEAC) (3.3mL, 0.9M, n (Al)/n (Pd)=600) add in reaction flask, design temperature is 10 DEG C and maintains reaction stirring after 15 minutes, add the o-dichlorobenzene solution that has dissolved nickel catalyzator (5 mmol) through syringe, regulate ethene intake to make the pressure of polymerization system maintain 0.02 MPa.At 20 DEG C, ethylene polymerization was carried out after 10 minutes, add 5% acidifying methyl alcohol termination reaction, then add 100 mL methyl alcohol vibrations, be settled out polymerisate.Precipitation leaves standstill after 24 hours and filters, and fully washs with anhydrous methanol, and 60 DEG C of vacuum-drying 48 hours, obtains polyethylene 1.0g, and activity is 1.00 × 10
6gPE/(mol Pd
h
bar).
(6) polymerisate is analyzed through differential thermal analysis (DSC) and gel permeation chromatography (GPC), and weight-average molecular weight is 2.01 × 10
5, number-average molecular weight is 1.75 × 10
5, molecular weight distribution 1.15, the degree of branching is 105 side chain/1000C.
Embodiment 4
(1) 4-normal-butyl-2, synthesizing of 6-dibromo aniline: take 4-n-butyl aniline (5.0mmol, 0.75g), add the methylene dichloride of 30ml, low-grade fever is dissolved it completely, then adds glacial acetic acid (2mL), ice-water bath is cooled to 5 DEG C, slowly splash into bromine (bromine (12.5mmol, 2.00g) is dissolved in methylene dichloride), stirring reaction 5h to reaction system.After question response finishes, slowly add 10% saturated aqueous sodium hydroxide solution neutralization, then use petroleum ether extraction organic phase (20mL × 3), anhydrous magnesium sulfate drying, filtering and concentrating, with silica gel column chromatography (ethyl acetate: sherwood oil=1:12(v/v)) separate, concentrate to obtain white solid 1.23g.Productive rate 80%.
1H NMR (400MHz, CDCl
3): δ 0.84 (t,
J=7.2 HZ, 3H, -CH
2-C
H 3), 1.20-1.29 (m, 2H, -C
H 2-CH
3), 1.41-1.51 (m, 2H, -C
H 2-CH
2-CH
3), 2.38 (t,
J=7.6 HZ, 2H, C
6H
2-C
H 2-), 4.32 (s, 2H, -N
H 2), 7.12 (s, 2H, C
6 H 2 -NH
2).
13C NMR (400 MHz, CDCl
3): δ 13.88 (-CH
2-
CH
3), 22.11 (-
CH
2-CH
3), 33.53 (-
CH
2-CH
2-CH
3), 34.07 (C
6H
2-
CH
2-), 108.71 (
C 6H
2-NH
2), 131.51 (
C 6H
2-NH
2), 134.52 (
C 6H
2-NH
2), 139.60 (
C 6H
2-NH
2)。
Its reaction formula is as follows:
(2) 4-normal-butyl-2, synthesizing of 6-phenylbenzene aniline: successively by palladium (0.04mmol, 0.01g), phenylo boric acid (4.4mmol, 0.54g), 4-chloro-2,6-dibromo aniline (2.0mmol, 0.57g) and salt of wormwood (4.0mmol, 0.55g) join in the PEG-4000 solvent of 20mL, add the water of 0.5ml, at room temperature stirring reaction 16 hours, uses extracted with diethyl ether after reaction again, extraction liquid anhydrous magnesium sulfate drying, filter, concentrated rear employing silica gel column chromatography separates and obtains 4-normal-butyl-2,6-phenylbenzene aniline 0.38g.Productive rate is 63%.
1H NMR (400MHz, CDCl
3): δ 0.85(t,
J=7.2 HZ, 3H, -CH
2-C
H 3), 1.26-1.35 (m, 2H, -C
H 2-CH
3), 1.49-1.57 (m, 2H, -C
H 2-CH
2-CH
3), 2.49 (t,
J=7.6 HZ, 2H, C
6H
2-C
H 2-), 3.70 (s, 2H, -N
H 2), 6.89 (s, 2H, C
6 H 2-NH
2), 7.27 (t,
J=7.6, 2H, C
6 H 5-), 7.37 (t,
J=7.6, 4H, C
6 H 5-), 7.44 (d,
J=7.2, 4H, C
6 H 5-).
13C NMR (400 MHz, CDCl
3): δ 13.99 (-CH
2-
CH
3), 22.34 (-
CH
2-CH
3), 33.91 (-
CH
2-CH
2-CH
3), 34.73 (C
6H
2-
CH
2-), 127.11 (
C 6H
2-NH
2), 128.06 (
C 6H
5-), 128.71 (
C 6H
5-), 129.29 (
C 6H
5-), 129.64 (
C 6H
2-NH
2), 132.72 (
C 6H
2-CH
2-), 138.06 (
C 6H
5-), 139.84 (
C 6H
2-NH
2)。
Its reaction formula is as follows:
(3) part (4-Bu-2,6-diPhPh)
2dABAn's is synthetic: by 4-normal-butyl-2,6-phenylbenzene aniline (2.2mmol, 0.66g) and acenaphthenequinone (1.0mmol, 0.18g) be dissolved in 20mL benzene, under agitation add p-methyl benzenesulfonic acid (0.1mmol, 20mg) to make catalyzer, at 88 DEG C, back flow reaction is after 36 hours, except desolventizing, by this thick silica gel column chromatography (ethyl acetate: sherwood oil=1:18(v/v) product for) separation, vacuum-drying obtains safran pulverulent solids 0.49g.Productive rate is 66%.
1H NMR (400 MHz, CDCl
3): δ 0.89 (t,
J=7.2 HZ, 6H, -CH
2-C
H 3), 1.31-141 (m, 4H, -C
H 2-CH
3), 1.58-1.71 (m, 4H, -C
H 2-CH
2-CH
3), 2.56-2.72 (m, 4H, C
6H
2-C
H 2-), 6.61-7.00 (m, 12H, C
6 H 5-), 7.02-7.19 (m, 8H, C
6 H 5-), 7.23 (d,
J=7.2 HZ, 4H, C
6 H 2-CH
2-), 7.28-7.31 (m, 2H, Nap-
H), 7.49 (d,
J=8.0 HZ, 2H, Nap-
H), 7.61 (d,
J=8.8 HZ, 2H, Nap-
H).
13C NMR (400 MHz, CDCl
3): δ 14.04 (-CH
2-
CH
3), 22.39 (-
CH
2-CH
3), 33.67 (-
CH
2-CH
2-CH
3), 35.06 (C
6H
2-
CH
2-), 122.48 (Nap-
C), 122.75 (Nap-
C), 126.33 (
C 6H
4-), 127.74 (
C 6H
2-CH
2-), 127.81 (
C 6H
4-), 127.91 (
C 6H
4-), 127.98 (
C 6H
2-CH
2-), 128.70 (
C 6H
4-), 129.17 (Nap-
C), 130.57 (Nap-
C), 131.21 (Nap-
C), 138.90 (Nap-
C), 139.92 (
C 6H
2-CH
2-), 144.58 (
C 6H
2-N=C), 160.98 (
C=N). Anal. Calcd. for C
56H
48N
2: C, 89.80; H, 6.46; N, 3.74. Found: C, 89.78; H, 6.49; N, 3.70。
Its reaction formula is as follows:
(4) title complex PdCl
2(4-Bu-2,6-diPhPh)
2dABAn's is synthetic:
Under nitrogen protection, in the dry reaction tubes of 100mL, add above-mentioned part (0.5mmol, 0.37g), then add PdCl
2(MeCN)
2(0.5mmol, 0.13g) and processed good methylene dichloride 30mL, reaction is at room temperature stirred 16 hours, filtering suspension liquid, mother liquor is except desolventizing under vacuum, and ether for residue (3 × 16mL) washing three times, obtains gray powder powder solid complexes 0.43g after vacuum-drying.Productive rate is 92%.
Anal. Calcd. For : C
56H
48Cl
2N
2Pd：C, 72.61; H, 5.22; N, 3.02. Found：C, 72.58; H, 5.25; N, 2.99。
Its reaction formula is as follows:
(5) vinyl polymerization: by the 250mL polymerization bottle vacuum with magnetic stick-nitrogen circulation displacement three times, under nitrogen atmosphere, add 50mL toluene solution, pass into again ethene, ethene is fully absorbed until saturated, then with being with graduated syringe by promotor diethylaluminum chloride (DEAC) (3.3mL, 0.9M, n (Al)/n (Pd)=600) add in reaction flask, design temperature is 10 DEG C and maintains reaction stirring after 15 minutes, add the o-dichlorobenzene solution that has dissolved nickel catalyzator (5 mmol) through syringe, regulate ethene intake to make the pressure of polymerization system maintain 0.02 MPa.At 20 DEG C, ethylene polymerization was carried out after 10 minutes, add 5% acidifying methyl alcohol termination reaction, then add 100 mL methyl alcohol vibrations, be settled out polymerisate.Precipitation leaves standstill after 24 hours and filters, and fully washs with anhydrous methanol, and 60 DEG C of vacuum-drying 48 hours, obtains polyethylene 1.1g, and activity is 1.10 × 10
6gPE/(molPd
h
bar).
(6) polymerisate is analyzed through differential thermal analysis (DSC) and gel permeation chromatography (GPC), and weight-average molecular weight is 1.53 × 10
5, number-average molecular weight is 1.08 × 10
5, molecular weight distribution 1.42, the degree of branching is 98 side chain/1000C.
Embodiment 5
(1) the fluoro-3-of 4-chloro-2, synthesizing of 6-dibromo aniline: take 4-n-butyl aniline (5.0mmol, 0.73g), add the methylene dichloride of 30ml, low-grade fever is dissolved it completely, then add glacial acetic acid (2mL), ice-water bath is cooled to 5 DEG C, slowly splashes into bromine (12.5mmol, 2.00g to reaction system, bromine is dissolved in methylene dichloride), stirring reaction 5h.After question response finishes, slowly add 10% sodium hydroxide solution neutralization, with petroleum ether extraction organic phase (20mL × 3), anhydrous magnesium sulfate drying, filtering and concentrating, silica gel column chromatography (ethyl acetate: sherwood oil=1:13(v/v)) separate, concentrate to obtain white solid 1.29g, productive rate 85%.
1H NMR (400MHz, CDCl
3): δ 4.44 (s, 2H, -N
H 2), 7.20 (d,
J=8.0 HZ, 1H, C
6 H-NH
2).
13C NMR (400 MHz, CDCl
3): δ 105.31 (
C 6H
2-NH
2), 109.40 (
C 6H
2-NH
2), 118.91 (
C 6H
2-NH
2), 140.06 (
C 6H
2-NH
2), 149.15 (
C 6H
2-NH
2), 157.58 (
C 6H
2-NH
2)。
Its reaction formula is as follows:
(2) the fluoro-3-of 4-chloro-2, synthesizing of 6-phenylbenzene aniline: successively by palladium (0.04mmol, 0.01g), phenylo boric acid (4.4mmol, 0.54g), the fluoro-3-of 4-chloro-2,6-dibromo aniline (2.0mmol, 0.57g) and salt of wormwood (4.0mmol, 0.55g) join in the PEG-4000 solvent of 20mL, add the water of 0.5ml, at room temperature stirring reaction 20 hours, uses extracted with diethyl ether after reaction again, extraction liquid anhydrous magnesium sulfate drying, filter, adopt silica gel column chromatography to separate after concentrated to obtain the fluoro-3-of 4-chloro-2,6-phenylbenzene aniline 0.38g.Productive rate is 64%.
1H NMR (400MHz, CDCl
3): δ 4.08 (s, 2H, -N
H 2), 6.83-6.88 (m, 1H, C
6 H-F), 7.24-7.44 (m, 10H, C
6 H 5-).
13C NMR (400 MHz, CDCl
3): δ 117.31 (
C 6H-NH
2), 119.00 (
C 6H-NH
2), 119.45 (
C 6H-NH
2), 125.62 (
C 6H-NH
2), 127.52 (
C 6H
5-), 127.88 (
C 6H
5-), 129.02 (
C 6H
5-), 136.53 (
C 6H
5-), 139.66 (
C 6H
5-), 141.46 (
C 6H-NH
2), 153.83 (
C 6H-NH
2)。
Its reaction formula is as follows:
(3) part (3-Cl-4-F-2,6-diPhPh)
2dABAn's is synthetic: by fluoro-4-3-chloro-2,6-phenylbenzene aniline (2.1mmol, 0.63g) and acenaphthenequinone (1.0mmol, 0.18g) be dissolved in 20mL benzene, under agitation add p-methyl benzenesulfonic acid (0.1mmol, 20mg) to make catalyzer, at 88 DEG C, back flow reaction is after 12 ~ 48 hours, except desolventizing, by this thick silica gel column chromatography (ethyl acetate: sherwood oil=1:20(v/v) product for) separation, vacuum-drying obtains safran pulverulent solids 0.51g.Productive rate is 69%.
1H NMR (400 MHz, CDCl
3): δ 6.76 (d,
J=6.8 HZ, 2H, C
6 H-F), 6.98-7.06 (m, 12H, C
6 H 5-), 7.18-7.41 (m, 8H, C
6 H 5-), 7.53-7.55 (m, 4H, Nap-
H), 7.74 (d,
J=8.4 HZ, 2H, Nap-
H).
13C NMR (400 MHz, CDCl
3):δ 117.86 (
C 6H-F), 119.96 (
C 6H-F), 123.68 (Nap-
C), 127.45 (Nap-
C), 127.63 (
C 6H
5-), 127.92 (
C 6H
5-), 129.21 (
C 6H
5-), 129.34 (Nap-
C), 130.58 (Nap-
C), 131.32 (Nap-
C), 131.58 (
C 6H-F), 132.64 (
C 6H-F), 136.51 (
C 6H
5-), 141.78 (Nap-
C), 148.02 (
C 6H-F), 161.28 (
C=N), 162.26 (
C 6H-F). Anal. Calcd. for C
48H
28Cl
2F
2N
2: C, 77.73; H, 3.81; N, 3.78. Found: C, 77.70; H, 3.79; N, 3.80。
Its reaction formula is as follows:
(4) title complex PdCl
2(3-Cl-4-F-2,6-diPhPh)
2dABAn's is synthetic:
Under nitrogen protection, in the dry reaction tubes of 100mL, add above-mentioned part (0.5mmol, 0.37g), then add PdCl
2(MeCN)
2(0.5mmol, 0.13g) and processed good methylene dichloride 30mL, reaction is at room temperature stirred 16 hours, filtering suspension liquid, mother liquor is except desolventizing under vacuum, and ether for residue (3 × 16mL) washing three times, obtains gray powder powder solid complexes 0.40g after vacuum-drying.Productive rate is 87%.
Anal. Calcd. For : C
48H
28Cl
4F
2N
2Pd：C, 62.73; H, 3.07; N, 3.05. Found：C, 62.71; H, 3.09; N, 3.00.
Its reaction formula is as follows:
(5) vinyl polymerization: by the 250mL polymerization bottle vacuum with magnetic stick-nitrogen circulation displacement three times, under nitrogen atmosphere, add 50mL toluene solution, pass into again ethene, ethene is fully absorbed until saturated, then with being with graduated syringe by promotor diethylaluminum chloride (DEAC) (3.3mL, 0.9M, n (Al)/n (Pd)=600) add in reaction flask, design temperature is 10 DEG C and maintains reaction stirring after 15 minutes, add the o-dichlorobenzene solution that has dissolved nickel catalyzator (5 mmol) through syringe, regulate ethene intake to make the pressure of polymerization system maintain 0.02 MPa.At 20 DEG C, ethylene polymerization was carried out after 10 minutes, add 5% acidifying methyl alcohol termination reaction, then add 100 mL methyl alcohol vibrations, be settled out polymerisate.Precipitation leaves standstill after 24 hours and filters, and fully washs with anhydrous methanol, and 60 DEG C of vacuum-drying 48 hours, obtains polyethylene 1.5g, and activity is 1.50 × 10
6gPE/(molPd
h
bar).
(6) polymerisate is analyzed through differential thermal analysis (DSC) and gel permeation chromatography (GPC), and weight-average molecular weight is 1.67 × 10
5, number-average molecular weight is 1.24 × 10
5, molecular weight distribution 1.35, the degree of branching is 115 side chain/1000C.
Claims (8)
1. the preparation method who contains alpha-diimine palladium (II) olefin polymerization catalysis of ortho position phenyl replacement, comprises following processing step:
(1) preparation of the aniline category matter that ortho position bromine replaces: taking methylene dichloride as solvent, aniline at room temperature reacts 20～30min with glacial acetic acid with the mol ratio of 1:1.5～1:6, obtains phenyl acetanilide,Phenacetylaniline class material; Add again the bromine of aniline molar weight 1:2.0～2.2 times, stirring reaction 3～5h at 0～5 DEG C; After reacting completely, except desolventizing, with strong base solution neutralization, then use petroleum ether extraction organic phase, anhydrous magnesium sulfate drying, filtering and concentrating, column chromatography for separation, obtains the aniline category matter that ortho position bromine replaces;
(2) preparation of the aniline category matter that ortho position phenyl replaces: taking PEG-400 as solvent, taking Palladous chloride as catalyzer, the aniline category matter that phenylo boric acid and ortho position bromine replace, with the mixed in molar ratio of 1:2.0～1:2.2, is adjusted pH=7～11 of system, stirring reaction 12～24 hours; After reacting completely, by extracted with diethyl ether, anhydrous magnesium sulfate drying, filters, concentrated, and silica gel column chromatography separates, and obtains the aniline category matter that ortho position phenyl replaces;
(3) preparation of the part with symmetrical schiff bases structure that contains ortho position phenyl replacement: taking benzene as solvent; taking p-methyl benzenesulfonic acid as catalyzer; the aniline category matter that ortho position phenyl is replaced and acenaphthenequinone are with the mixed in molar ratio of 2.0:1～2.2:1; at 80～90 DEG C, back flow reaction is after 12～48 hours; except desolventizing; silica gel column chromatography separates, and vacuum-drying obtains part;
(4) preparation of alpha-diimine palladium (II) olefin polymerization catalysis that contains ortho position phenyl replacement: under nitrogen protection, taking methylene dichloride as solvent, ortho position the phenyl part with symmetrical schiff bases structure replacing and the Palladous chloride being activated by the acetonitrile mixed in molar ratio with 1:1～1:1.2 will be contained, at room temperature stirring reaction is after 12～24 hours, filtering suspension liquid, mother liquor except after desolventizing, washs with ether under vacuum condition, vacuum-drying, obtains pulverulent solids title complex;
Described alpha-diimine palladium (II) olefin polymerization catalysis that contains ortho position phenyl replacement, its structure is:
Wherein, R
1for halogen, C1～C4 alkyl; R
2for halogen, hydrogen.
2. the preparation method who contains as claimed in claim 1 alpha-diimine palladium (II) olefin polymerization catalysis of ortho position phenyl replacement, is characterized in that: the eluent that the described column chromatography for separation of step (1) adopts is to be mixed with the volume ratio of 1:5～1:15 with sherwood oil by ethyl acetate.
3. contain as claimed in claim 1 the preparation method of alpha-diimine palladium (II) olefin polymerization catalysis of ortho position phenyl replacement, it is characterized in that: the aniline category matter that the described ortho position of step (2) bromine replaces is 4-fluoro-2,6-dibromo aniline, 4-is chloro-2,6-dibromo aniline, the fluoro-3-of 4-chloro-2,6-dibromo aniline, 4-methyl-2,6-dibromo aniline, 4-normal-butyl-2,6-dibromo aniline.
4. the preparation method who contains as claimed in claim 1 alpha-diimine palladium (II) olefin polymerization catalysis of ortho position phenyl replacement, is characterized in that: in step (2), the consumption of catalyzer Palladous chloride is 0.5～4% of phenylo boric acid molar weight.
5. the preparation method who contains as claimed in claim 1 alpha-diimine palladium (II) olefin polymerization catalysis of ortho position phenyl replacement, is characterized in that: it is to be mixed with the volume ratio of 1:15～1:30 with sherwood oil by ethyl acetate that the described silica gel column chromatography of step (2) separates the eluent adopting.
6. the preparation method who contains as claimed in claim 1 alpha-diimine palladium (II) olefin polymerization catalysis of ortho position phenyl replacement, is characterized in that: in step (3), the consumption of catalyzer p-methyl benzenesulfonic acid is 2～10% of acenaphthenequinone molar weight.
7. contain as claimed in claim 1 the preparation method of alpha-diimine palladium (II) olefin polymerization catalysis of ortho position phenyl replacement, it is characterized in that: in step (3), the eluent that silica gel column chromatography separates is to be mixed with the volume ratio of 1:10～1:25 with sherwood oil by ethyl acetate.
8. contain as claimed in claim 1 the preparation method of alpha-diimine palladium (II) olefin polymerization catalysis of ortho position phenyl replacement, it is characterized in that: the preparation method of the Palladous chloride being activated by acetonitrile described in step (4) is: the mixed in molar ratio by Palladous chloride and acetonitrile with 1:8～1:50,5～10h refluxes at 60～70 DEG C, filter, concentrated, vacuum-drying, obtains pulverulent solids PdCl
2(MeCN)
2.
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| CN105482000B (en) * | 2014-09-18 | 2018-06-15 | 中国石油化工股份有限公司 | A kind of olefin polymerization catalysis and its methods for making and using same |
| CN105152970B (en) * | 2015-06-25 | 2017-04-12 | 中国科学技术大学 | Diimine palladium catalyst with great steric hindrance, and ligand, preparation method and application thereof |
| US10370521B2 (en) | 2016-11-11 | 2019-08-06 | The Board Of Trustees Of The University Of Illinois | Methods for synthesis of polyolefin-containing block copolymers |
| CN107698699B (en) * | 2017-09-27 | 2021-01-29 | 常州大学 | Nickel (II) complexes containing p-benzhydryl substituted alpha-diimines for the catalysis of the polymerization of ethylene and 2-hexene |
| CN109053818B (en) * | 2018-08-10 | 2021-05-04 | 常州大学 | Preparation of fluorinated nickel (II) complexes containing ortho-diphenylmethyl-substituted alpha-diimines for ethylene polymerization |
| CN110283214A (en) * | 2019-06-28 | 2019-09-27 | 江苏高科石化股份有限公司 | A kind of alpha-diimine palladium (II) catalyst and preparation method thereof replaced containing contraposition benzhydryl |
| CN110317149B (en) * | 2019-07-31 | 2022-08-09 | 安徽大学 | Large steric hindrance flexible diimine ligand, nickel diimine and palladium complex based on ligand, and catalytic application of nickel diimine and palladium complex |
| CN110511251B (en) * | 2019-08-20 | 2021-01-26 | 中山大学 | Alpha-nickel diimine complex, metal catalyst, branched polyethylene wax, and preparation method and application thereof |
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