CN102775448A - Post-transition metal complex, preparation method thereof and polyethylene preparation method - Google Patents

Post-transition metal complex, preparation method thereof and polyethylene preparation method Download PDF

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CN102775448A
CN102775448A CN2012102991103A CN201210299110A CN102775448A CN 102775448 A CN102775448 A CN 102775448A CN 2012102991103 A CN2012102991103 A CN 2012102991103A CN 201210299110 A CN201210299110 A CN 201210299110A CN 102775448 A CN102775448 A CN 102775448A
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transition metal
metal complex
preparation
hydrogen
formula
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CN102775448B (en
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张学全
刘恒
白晨曦
张春雨
代全权
蔡洪光
那丽华
毕吉福
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a post-transition metal complex having a structure shown in a formula (I). The invention also provides a preparation method of the post-transition metal complex, which comprises the following steps: performing first reaction on di(substituted phenylamine)-2,6-pyridine dicarboxamide and phosphorous pentachloride in a first organic solvent to obtain a ligand having a structure shown in a formula (II); and performing second reaction on the ligand and post-transition metal halide in a second organic solvent to obtain the post-transition metal complex having the structure shown in the formula (I). The invention also provides a polyethylene preparation method which comprises the following specific step: under the effects of a cocatalyst and the post-transition metal complex having the structure shown in the formula (I), performing polymerization reaction on ethylene in an organic solvent to obtain polyethylene. The post-transition metal complex provided by the invention has high catalytic activity in catalytic ethylene polymerization.

Description

Late transition metal complex and preparation method thereof and poly preparation method
Technical field
The present invention relates to catalyst technical field, relate in particular to late transition metal complex and preparation method thereof and poly preparation method.
Background technology
The development of polyolefin industry is the important symbol of a national petrochemical industry development.Ziegler-Natta catalyst, metallocene catalyst and late transition metal catalyst are 3 main directions of olefin polymerization catalysis research.Because rear transition metal has low price, characteristics such as environmental friendliness have obtained tremendous development based on the late transition metal catalyst of olefinic polymerization in recent years, and post-transition metal catalyst system becomes the focus of research gradually.
Brookhart etc. have invented alpha-diimine NN bidentate system; It selects Ni for use, and Pd has shown good active as central metal for vinyl polymerization; And utilize this system to realize the copolymerization of ethene and polar monomer first, shown unique polymerization behavior.Nagashima etc. have invented β-diimine NN bidentate system, and it selects for use Co as central metal, and catalyzed ethylene polymerization has obtained ultra high molecular weight polyethylene.But above-mentioned bidentate System Catalyst structure is unstable relatively, and is wayward in ethylene polymerization, thereby limited the development of such catalyzer.
Discover that three toothings are stable, ligand structure is prone to modify, so NNN tridentate pyridine diimine transition metal system catalyzed ethylene polymerization has received extensive concern.At present; The research of NNN tridentate pyridine diimine transition-metal catalyst mainly concentrates on two aspects: 1) through regulating the substituting group on the aniline phenyl ring; Obtain having the NNN three tooth transition metal complexes of different steric hindrances and electronic effect; And utilize the metal complexes catalyzed ethylene polymerization of different structure, thereby reach the purpose of regulating Polyethylene Chain structure and molecular weight; 2) through changing metal center, obtain the Vilaterm of different structure and molecular weight.For example: Gibson etc. are with methoxyl group, and methylthio group is introduced skeleton structure, has synthesized corresponding Fe (II) complex compound, and catalyzed ethylene polymerization shows good active; S.Damavandi etc. introduce nitro in the skeleton structure, and catalyzed ethylene polymerization has obtained ultra high molecular weight polyethylene.But during existing late transition metal complex catalyzed ethylene polymerization, the catalytic activity of late transition metal complex is still lower.Thus, the inventor has considered a kind of novel NNN tridentate pyridine diimine transition metal compound catalizer.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of late transition metal complex with greater activity and preparation method thereof.
In view of this, the invention provides a kind of late transition metal complex with formula I structure,
Figure BDA00002037852600021
Wherein, R 1And R 2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R 3Alkyl for hydrogen, halogen or C1 ~ C10;
Mt is Co (II), Fe (II) or Ni (II);
X is a halogen.
Preferably, said R 1And R 2Independently be selected from hydrogen, methyl, ethyl or sec.-propyl separately.
Preferably, said R 3Be hydrogen, halogen, methyl, ethyl or sec.-propyl.
Preferably, said X is Cl or Br.
The present invention also provides a kind of preparation method of late transition metal complex, may further comprise the steps:
With two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride carry out first set reaction, the part that obtains having the formula II structure in first organic solvent;
The halogenide of said part and rear transition metal is carried out the reaction second time at second organic solvent, and the late transition metal complex that obtains having the formula I structure, said rear transition metal are cobalt, iron or nickel;
Figure BDA00002037852600031
Wherein, R 1And R 2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R 3Alkyl for hydrogen, halogen or C1 ~ C10;
Mt is Co (II), Fe (II) or Ni (II);
X is a halogen.
Preferably, said two (substituted aniline)-2, the mol ratio of 6-pyridine diformamide and said phosphorus pentachloride is 1: (1.5 ~ 2.5).
The present invention also provides a kind of poly preparation method, it is characterized in that, comprising:
Under the effect of promotor and late transition metal complex with formula I structure, ethene is carried out polyreaction in organic solvent, obtain Vilaterm;
Figure BDA00002037852600032
Wherein, R 1And R 2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R 3Alkyl for hydrogen, halogen or C1 ~ C10;
Mt is Co (II), Fe (II) or Ni (II);
X is a halogen.
Preferably, said promotor is a MAO.
Preferably, said organic solvent is a toluene.
Preferably, the time of said reaction is 0.3 ~ 1h.
The invention provides a kind of late transition metal complex and preparation method thereof with formula I structure; The present invention also provides a kind of poly preparation method; Under the effect of promotor and late transition metal complex with formula I structure; Ethene is carried out polyreaction in organic solvent, obtain Vilaterm.The present invention is incorporated into the chlorine atom in the pyridine diimine skeleton structure; Through part, organic solvent and the rear transition metal halide reaction that will have the formula II structure; The rear transition metal element is incorporated into the active site of pyridine diimine; Because the chlorine atom has very strong sucting electronic effect, can increase the positive polarity of center rear transition metal atom, can also make the angle of two phenyl ring in the title complex skeleton structure become big simultaneously; Carry out coordination thereby help the ethene atom, improve the activity of catalyzed ethylene polymerization.Experiment showed, late transition metal complex in the process of catalyzed ethylene polymerization, catalytic activity is 300 ~ 1000Kg PEmol -1H -1
Description of drawings
Fig. 1 is the crystalline structure figure that the X-single crystal diffraction of the title complex 5 of the embodiment of the invention 1 preparation characterizes;
Fig. 2 is the crystalline structure figure that the X-single crystal diffraction of the title complex 10 of the embodiment of the invention 2 preparations characterizes;
Fig. 3 is the crystalline structure figure that the X-single crystal diffraction of the title complex 21 of the embodiment of the invention 3 preparations characterizes;
Fig. 4 is the crystalline structure figure that the X-single crystal diffraction of the title complex 31 of the embodiment of the invention 4 preparations characterizes.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of late transition metal complex with formula I structure,
Figure BDA00002037852600051
Wherein, R 1And R 2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R 3Alkyl for hydrogen, halogen or C1 ~ C10;
Mt is Co (II), Fe (II) or Ni (II);
X is a halogen.
In the late transition metal complex provided by the invention; The chlorine element has been introduced in the pyridine diimine skeleton structure; Mt-N (C=N) bond distance is obviously increased; The positive polarity of proof Mt center reactive metal has certain increase, carries out coordination thereby help the ethene atom, and then catalyzed ethylene polymerization has higher activity.
In the above-mentioned late transition metal complex, said R 1And R 2Be the substituting group on the aniline, independently be preferably hydrogen, methyl, ethyl or sec.-propyl separately, more preferably hydrogen, methyl or sec.-propyl.Said R 3Be similarly the substituting group on the aniline, be preferably hydrogen, halogen or methyl, ethyl or sec.-propyl, more preferably hydrogen, chlorine, bromine or methyl.In the above-mentioned late transition metal complex, R 3During for halogen, R 3Same kind of halogen can be with X, also different halogens, for example R can be 3During for Cl, X can be Br.
Said Mt is the center active atomic, and Mt is a rear transition metal, and said rear transition metal and early transition metal are how much distinguishing according to d orbital electron number.Well known to those skilled in the art, said early transition metal is that d layer electronic number is no more than 5 transition metal, like Sc, V, Ti or Cr etc.; Said rear transition metal is that d layer electronic number surpasses 5 transition metal, for example, and Fe, Co, Ni or Mn etc.The rear transition metal that late transition metal complex of the present invention adopts is Fe, Co or Ni.
According to the present invention, said late transition metal complex with formula I structure is specially title complex 1 ~ title complex 40, and is as shown in table 1, and table 1 is the concrete title complex table with late transition metal complex of formula I structure,
Table 1 is the concrete title complex table with late transition metal complex of formula I structure
Figure BDA00002037852600071
The present invention also provides the preparation method of late transition metal complex, specifically preparation as follows:
With two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride carry out first set reaction, the part that obtains having the formula II structure in first organic solvent;
The halogenide of said part and rear transition metal is carried out the reaction second time in second organic solvent, the late transition metal complex that obtains having the formula I structure, said rear transition metal are cobalt, iron or nickel;
Figure BDA00002037852600081
Wherein, R 1And R 1Independently be selected from the alkyl of hydrogen or C 1 ~ C 10 separately;
R 3Alkyl for hydrogen, halogen or C 1 ~ C 10;
Obtain having the process of the part of formula II structure, be specially:
Under nitrogen protection, with two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride are added in the methylene dichloride, and back flow reaction obtains mix products, with mix products extraction, recrystallization, the part that promptly obtains having the formula II structure.
Said two (substituted aniline)-2, the mol ratio of 6-pyridine diformamide and said phosphorus pentachloride is preferably 1:1.5 ~ 2.5,1:2 more preferably, the time of said back flow reaction is preferably 3 ~ 5h, more preferably 3.5 ~ 4.5h.
After obtaining said part, the halogenide of said part and rear transition metal is carried out the reaction second time, the late transition metal complex that obtains having the formula I structure in second organic solvent.Said second organic solvent is preferably THF.The time of said reaction is preferably 3 ~ 7h, more preferably 4 ~ 6h.
According to the present invention, the halogenide of said part, said rear transition metal and the said second organic solvent blended be not restriction in proper order, can the halogenide of said part, said rear transition metal and said second organic solvent be added simultaneously to react.Equally also can said part be dissolved in second organic solvent; The halogenide of said rear transition metal is dissolved in second organic solvent; The halid drips of solution of rear transition metal that will be dissolved in second organic solvent then adds in the ligand solution that is dissolved in second organic solvent, reacts.Thorough for the halide reaction that makes said part and said rear transition metal, the present invention preferably adopts the back to plant hybrid mode.
The present invention is incorporated into halogen atom in the skeleton structure of pyridine diimine; Through with do not make comparisons with the late transition metal complex of chlorine, halogen atom is incorporated into after the skeleton structure, Mt-N (C=N) bond distance obviously increases; Center reactive metal atom positive polarity is increased; Can also make that simultaneously the angle of two phenyl ring becomes big in the title complex skeleton structure, carry out coordination thereby more help the ethene atom, catalyzed ethylene polymerization has higher activity.Have in the process of late transition metal complex of formula I structure in preparation; The halide reaction of part, organic solvent and rear transition metal through will having the formula II structure; The rear transition metal element is incorporated into the active site of pyridine diimine, has promptly obtained said late transition metal complex.
With said late transition metal complex provided by the invention as catalyst applications in the preparation catalyzed ethylene polymerization, in polymerization process, catalyzer has shown advantages of high catalytic activity, the process that the present invention prepares ethene is specially:
Ethene, promotor and late transition metal complex with formula I structure are carried out polyreaction in organic solvent, obtain Vilaterm;
Figure BDA00002037852600091
Wherein, R 1And R 2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R 3Alkyl for hydrogen, halogen or C1 ~ C10;
Mt is Co (II), Fe (II) or Ni (II);
X is a halogen.
According to the present invention, said ethene and said late transition metal complex blended be not restriction in proper order, can said ethene, organic solvent, promotor and late transition metal complex be added simultaneously and carry out polyreaction.Equally also can respectively ethene be dissolved in the organic solvent, obtain first solution, promotor is dissolved in the organic solvent; Obtain second solution, rear transition metal is dissolved in the organic solvent, obtain the 3rd solution; Three kinds of solution that obtain are mixed, carry out polyreaction.For said ethene, promotor and late transition metal complex are fully dissolved, the present invention preferably adopts the back to plant the adding mode.Simultaneously, for polyreaction is abundant, in the process of said polyreaction, guarantee that preferably ethene constantly supplies with.
Said organic solvent is preferably toluene.In above-mentioned polymerization process, if said rear transition metal exist singly does not have higher activity, need to add promotor, could guarantee said late transition metal complex and said promotor acting in conjunction, thereby have advantages of high catalytic activity.Said promotor is the promotor of catalyzed polyethylene well known to those skilled in the art, and the present invention preferably adopts MAO.The time of said polyreaction is preferably 0.3 ~ 1h, more preferably 0.5 ~ 0.8h.After above-mentioned polyreaction is carried out for some time, preferably polymerization liquid is poured in the mixed solution of ethanol and hydrochloric acid and stopped polymerization, after the filtration, promptly obtain Vilaterm.Experiment shows that the late transition metal complex with formula I structure is in the process of catalyzed ethylene polymerization, and activity is 300 ~ 1000kg PEmol -1H -1
In order further to understand the present invention, below in conjunction with embodiment late transition metal complex provided by the invention and poly preparation method are elaborated, protection scope of the present invention is not limited by the following examples.
Embodiment 1
8.11g (60mmol) 2 and 8.36ml (60mmol) triethylamine are dissolved in 50mlCH 2Cl 2In, 6.1g (30mmol) pyridine dimethyl chloride is dissolved in 20mlCH 2Cl 2In, with pyridine dimethyl chloride/CH 2Cl 2Drips of solution adds to substituted aniline/CH 2Cl 2In, reflux after 4 hours, use 100ml water and 100ml1.5M NaCO respectively 3Solution washing adopts separating funnel to obtain the CH of lower floor 2Cl 2Solution adds MgSO 4Dried overnight is filtered and is drained, and carries out recrystallization with toluene then, and filtration drying promptly gets product (5a).Productive rate 91%.(5a) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following: 1H NMR (400MHz, CDCl 3, δ, ppm): 9.02 (s, 2H, NH), 8.51 (d, 2H, Pyr-H m), 8.14 (t, 1H, Pyr-H p), 6.95 (s, 4H, Ar-H), 2.30 (s, 6H, Ar-C pH 3), 2.26 (s, 12H, Ar-C oH 3); 13C NMR (100MHz, CDCl 3, δ, ppm): 161.6,148.8,139.3,137.1,134.8,130.5,128.9,125.5,20.9,18.4.Hence one can see that, and product (5a) can prepare.
With product (5a) 5g (12.46mmol) and PCl 55.19g (24.92mmol) in the 100ml round-bottomed flask, add the 100ml methylene dichloride afterwards, reflux after three hours; Drain, adopt hot heptane extraction, obtain lurid n-heptane solution; Decompression is evacuated to saturated back recrystallization, promptly gets yellow powder product (5b), productive rate 44.6%.(5b) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following: 1H NMR (400MHz, CDCl 3, δ, ppm): 8.49 (d, 2H, Pyr-H m), 8.01 (t, 1H, Pyr-H o), 6.94 (s, 4H, Ar-H), 2.32 (s, 6H, Ar-C pH 3), 2.10 (s, 12H, Ar-C oH 3). 13C?NMR（100MHz，CDCl 3，δ，ppm）:151.2，145.2，143.4，137.6，134.0，128.6，125.8，125.6，20.8，17.8。IR（KBr，cm -1）：1658（v C=N）。Hence one can see that, and product (5b) can prepare.Above-mentioned reaction process is shown below:
Figure BDA00002037852600111
With 0.13g (1mmol) CoCl 2Be dissolved in and obtain blue suspension liquid among the 3mlTHF, part two (2) pyridine dicarboximide acyl chlorides 0.44g (1mmol) is dissolved among the 5ml THF, with part/THF solution at CoCl 2Drip in/THF the solution, stir 2h, obtain green suspension, cross and filter green powder, promptly get required title complex.Dry 0.4g, the productive rate 70.2% of getting.IR（KBr，cm -1）：1626（v C=N）。Crystalline structure figure sees accompanying drawing 1.Above-mentioned reaction process is as follows:
Figure BDA00002037852600112
Embodiment 2
With 11.94g (60mmol) 4-bromo-2,6-xylidine and 8.36ml (60mmol) triethylamine is dissolved in 50ml CH 2Cl 2In, 6.1g (30mmol) pyridine dimethyl chloride is dissolved in 20mlCH 2Cl 2In, with pyridine dimethyl chloride/CH 2Cl 2Drips of solution adds to substituted aniline/CH 2Cl 2In, reflux after 4 hours, use 100ml water and 100ml 1.5M NaCO respectively 3Solution washing obtains the CH of lower floor with separating funnel 2Cl 2Solution adds MgSO 4Dried overnight is filtered and is drained, and carries out recrystallization with toluene then, and filtration drying promptly gets product (10a), productive rate 86.4%.(10a) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following: 1H NMR (400MHz, CDCl 3, δ, ppm): 8.98 (s, 2H, NH), 8.55 (d, 2H, Pyr-H m), 8.19 (t, 1H, Pyr-H o), 7.33 (s, 4H, Ar-H), 2.30 (s, 12H ,-CH 3); 13C NMR (100MHz, CDCl 3, δ, ppm): 161.5,148.6,139.5,137.4,131.0,128.2,125.8,120.9,18.2.Hence one can see that, and product (10a) can prepare.
With product (10a) 6.62g (12.46mmol) and PCl 55.19g (24.92mmol) in the 100ml round-bottomed flask, add the 100ml methylene dichloride afterwards, reflux after three hours; Drain,, get lurid n-heptane solution with hot heptane extraction; Decompression is evacuated to saturated back recrystallization, promptly gets yellow powder product (10b), productive rate 44.6%.(10b) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following: 1H NMR (400MHz, CDCl 3, δ, ppm): 8.49 (d, 2H, Pyr-H m), 8.03 (t, 1H, Pyr-H o), 7.25 (s, 4H, Ar-H), 2.10 (s, 12H ,-CH 3); 13C NMR (100MHz, CDCl 3, δ, ppm): 150.8,146.0,144.7,137.6,130.5,128.1,125.6,117.3,17.5.IR（KBr，cm -1）:1655（v C=N）。Hence one can see that, and product (10b) can prepare.Above-mentioned reaction process is as follows:
Figure BDA00002037852600121
With 0.13g (1mmol) CoCl 2Be dissolved in and obtain blue suspension liquid among the 3mlTHF, pyridine dicarboximide acyl chlorides 0.57g (1mmol) is dissolved among the 5ml THF with part two (4-bromo-2,6-xylidine), and part/THF drips of solution is added to CoCl 2In/THF the solution, stir 2h, obtain green suspension, cross and filter green powder, promptly get required title complex.Dry 0.61g, the productive rate 87.1% of getting.IR（KBr，cm -1）：1624（v C=N）。Crystalline structure figure sees accompanying drawing 2.Above-mentioned reaction process is as follows:
Figure BDA00002037852600122
Embodiment 3
11.94g (60mmol) 2 and 8.36ml (60mmol) triethylamine are dissolved in 50ml CH 2Cl 2In, 6.1g (30mmol) pyridine dimethyl chloride is dissolved in 20mlCH 2Cl 2In, with pyridine dimethyl chloride/CH 2Cl 2Drips of solution adds to substituted aniline/CH 2Cl 2In, reflux after 4 hours, use 100ml water and 100ml 1.5M NaCO respectively 3Solution washing obtains the CH of lower floor with separating funnel 2Cl 2Solution adds MgSO 4Dried overnight is filtered and is drained, and carries out recrystallization with toluene then, and filtration drying promptly gets product (21a), productive rate 86.4%.(21a) carries out nuclear magnetic resonance spectroscopy with product, and characterization result is following: 1H NMR (400MHz, CDCl 3, δ, ppm): 8.98 (s, 2H, NH), 8.55 (d, 2H, Pyr-H m), 8.19 (t, 1H, Pyr-H o), 7.33 (s, 4H, Ar-H), 2.30 (s, 12H ,-CH 3). 13C?NMR（100MHz，CDCl 3，δ，ppm）：161.5，148.6，139.5，137.4，131.0，128.2，125.8，120.9，18.2。Hence one can see that, and product (21a) can prepare.
With product (21a) 6.62g (12.46mmol) and PCl 55.19g (24.92mmol) in the 100ml round-bottomed flask, add the 100ml methylene dichloride afterwards, reflux after three hours; Drain,, get lurid n-heptane solution with hot heptane extraction; Decompression is evacuated to saturated back recrystallization, promptly gets yellow powder product (21b), productive rate 44.6%.(21b) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following: 1H NMR (400MHz, CDCl 3, δ, ppm): 8.49 (d, 2H, Pyr-H m), 8.03 (t, 1H, Pyr-H o), 7.25 (s, 4H, Ar-H), 2.10 (s, 12H ,-CH 3) .13C NMR (100MHz, CDCl 3, δ, ppm): 150.8,146.0,144.7,137.6,130.5,128.1,125.6,117.3,17.5.IR（KBr，cm -1）:1655（v C=N）。Hence one can see that, and product (21b) can prepare.Above-mentioned reaction process is as follows:
With 0.13g (1mmol) NiCl 2Be dissolved in and obtain blue suspension liquid among the 3mlTHF, part two (2) pyridine dicarboximide acyl chlorides 0.57g (1mmol) is dissolved among the 5ml THF, part/THF drips of solution is added to NiCl 2In/THF the solution, stir 2h, obtain brown suspension, cross and filter brown ceramic powder, promptly get required title complex, dry 0.58g, the productive rate 86.5% of getting.IR（KBr，cm -1）:1624（v C=N）。Crystalline structure figure sees accompanying drawing 3.Above-mentioned reaction is as follows:
Figure BDA00002037852600141
Embodiment 4
11.94g (60mmol) 2 and 8.36ml (60mmol) triethylamine are dissolved in 50ml CH 2Cl 2In, 6.1g (30mmol) pyridine dimethyl chloride is dissolved in 20ml CH 2Cl 2In, with pyridine dimethyl chloride/CH 2Cl 2Drips of solution adds to substituted aniline/CH 2Cl 2In, reflux after 4 hours, use 100ml water and 100ml 1.5M NaCO respectively 3Solution washing obtains the CH of lower floor with separating funnel 2Cl 2Solution adds MgSO 4Dried overnight is filtered and is drained, and carries out recrystallization with toluene then, and filtration drying promptly gets product (31a), productive rate 86.4%.(31a) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following: 1H NMR (400MHz, CDCl 3, δ, ppm): 8.98 (s, 2H, NH), 8.55 (d, 2H, Pyr-H m), 8.19 (t, 1H, Pyr-H o), 7.33 (s, 4H, Ar-H), 2.30 (s, 12H ,-CH 3). 13C NMR (100MHz, CDCl 3, δ, ppm): 161.5,148.6,139.5,137.4,131.0,128.2,125.8,120.9,18.2.Hence one can see that, and product (31a) can prepare.
With product (31a) 6.62g (12.46mmol) and PCl 55.19g (24.92mmol) in the 100ml round-bottomed flask, add the 100ml methylene dichloride afterwards, reflux after three hours; Drain,, get lurid n-heptane solution with hot heptane extraction; Decompression is evacuated to saturated back recrystallization, promptly gets yellow powder product (31b), productive rate 44.6%.(31b) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following: 1H NMR (400MHz, CDCl 3, δ, ppm): 8.49 (d, 2H, Pyr-H m), 8.03 (t, 1H, Pyr-H o), 7.25 (s, 4H, Ar-H), 2.10 (s, 12H ,-CH 3). 13C?NMR（100MHz，CDCl 3，δ，ppm）:150.8，146.0，144.7，137.6，130.5，128.1，125.6，117.3，17.5。IR（KBr，cm -1）：1655（v C=N）。Hence one can see that, and product (31b) can prepare.Above-mentioned reaction process is as follows:
With 0.154g (1mmol) NiBr 2DME is dissolved in and obtains blue suspension liquid among the 3mlTHF, and part two (2) pyridine dicarboximide acyl chlorides 0.219g (1mmol) is dissolved among the 5ml THF, and part/THF drips of solution is added to NiBr 2In/THF the solution, stir 2h, obtain brown suspension, cross and filter brown ceramic powder, promptly get required title complex, dry 0.25g, the productive rate 72.6% of getting.IR（KBr，cm -1）：1624（v C=N）。Crystalline structure figure sees accompanying drawing 4.Above-mentioned reaction process is as follows:
Embodiment 5
Basic identical with the preparation method of embodiment 1, difference is: with 1mmol FeCl 2Be dissolved in and obtain blue suspension liquid among the 3mlTHF, part two (2) pyridine dicarboximide acyl chlorides 0.44g (1mmol) is dissolved among the 5ml THF, with part/THF solution at FeCl 2Drip in/THF the solution, stir 2h, obtain green suspension, cross and filter green powder, promptly get title complex 15 with formula II structure.
Figure BDA00002037852600153
Embodiment 6
Basic identical with the preparation method of embodiment 2, difference is: with 1mmol FeCl 2Be dissolved in and obtain blue suspension liquid among the 3mlTHF, pyridine dicarboximide acyl chlorides 0.57g (1mmol) is dissolved among the 5ml THF with part two (4-bromo-2,6-xylidine), and part/THF drips of solution is added to FeCl 2In/THF the solution, stir 2h, obtain green suspension, cross and filter green powder, promptly get title complex 20 with formula III structure.
Figure BDA00002037852600161
Embodiment 7
In the 100ml reaction vessel, add 45ml toluene, fill ethene with the nitrogen ball, and make the toluene solvant unsaturated ethylene, be placed on then in 20 ℃ of oil baths, adding 3.33ml concentration is the toluene solution of the MAO (MAO) of 1.5M, stirs 2 minutes.Take by weighing 2.93 * 10 -3G cooperates 5, is dissolved in the 5ml toluene solution, and catalyzer is imported in ethene/toluene solution, and polymerization begins.Behind the 20min, reaction terminating, polymkeric substance suspension liquid are poured in the mixed solution of ethanol and hydrochloric acid, and the Vilaterm deposition is separated out, and uses washing with alcohol, and filtration drying gets polyethylene product.Get 1.487g.Polymerization activity is 892.2Kg PEmol -1H -1Poly molecular weight is 790, MWD 4.23.
Embodiment 8
In the 100ml reaction vessel, add 45ml toluene, fill ethene with the nitrogen ball, and make the toluene solvant unsaturated ethylene, be placed on then in 20 ℃ of oil baths, adding 3.33ml concentration is the toluene solution of the MAO of 1.5M, stirs 2 minutes.Take by weighing 3.49 * 10 -3 G title complex 10 is dissolved in the 5ml toluene solution, and catalyzer is imported in ethene/toluene solution, and polymerization begins.Behind the 20min, reaction terminating, the polymkeric substance suspension liquid is poured in the mixed solution of ethanol and hydrochloric acid, and polyethylene particle is separated out, and uses washing with alcohol, and filtration drying gets the 0.889g polyethylene product.Activity is 533.4KgPEmol -1H -1Poly molecular weight is 1040, and MWD is 2.16.
Embodiment 9
In the 100ml reaction vessel, add 45ml toluene, fill ethene with the nitrogen ball, and make the toluene solvant unsaturated ethylene, be placed on then in 20 ℃ of oil baths, adding 3.33ml concentration is the toluene solution of the MAO of 1.5M, stirs 2 minutes.Take by weighing 2.85 * 10 -3 G title complex 15 is dissolved in the 5ml toluene solution, and catalyzer is imported in ethene/toluene solution, and polymerization begins.Behind the 20min, reaction terminating, the polymkeric substance suspension liquid is poured in the mixed solution of ethanol and hydrochloric acid, and polyethylene particle is separated out, and uses washing with alcohol, and filtration drying gets the 0.862g polyethylene product.Activity is 517.2KgPEmol -1H -1Poly molecular weight is 980, and MWD is 5.72.
Embodiment 10
In the 100ml reaction vessel, add 45ml toluene, fill ethene with the nitrogen ball, and make the toluene solvant unsaturated ethylene, be placed on then in 20 ℃ of oil baths, adding 3.33ml concentration is the toluene solution of the MAO of 1.5M, stirs 2 minutes.Take by weighing 3.5 * 10 -3 G title complex 20 is dissolved in the 5ml toluene solution, and catalyzer is imported in ethene/toluene solution, and polymerization begins.Behind the 20min, reaction terminating, the polymkeric substance suspension liquid is poured in the mixed solution of ethanol and hydrochloric acid, and polyethylene particle is separated out, and uses washing with alcohol, and filtration drying gets the 1.6608g polyethylene product.Activity is 996.5KgPEmol -1H -1Poly molecular weight is 2370, and MWD is 16.45.
Embodiment 11
In the 100ml reaction vessel, add 45ml toluene, fill ethene with the nitrogen ball, and make the toluene solvant unsaturated ethylene, be placed on then in 40 ℃ of oil baths, adding 3.33ml concentration is the toluene solution of the MAO of 1.5M, stirs 2 minutes.Take by weighing 2.93 * 10 -3 G title complex 5 is dissolved in the 5ml toluene solution, and catalyzer is imported in ethene/toluene solution, and polymerization begins.Behind the 20min, reaction terminating, the polymkeric substance suspension liquid is poured in the mixed solution of ethanol and hydrochloric acid, and polyethylene particle is separated out, and uses washing with alcohol, and filtration drying gets the 1.257g polyethylene product.Activity is 754.6KgPEmol -1H -1Poly molecular weight is 920, and MWD is 2.17.
Embodiment 12
In the 100ml reaction vessel, add 45ml toluene, fill ethene with the nitrogen ball, and make the toluene solvant unsaturated ethylene, be placed on then in 60 ℃ of oil baths, adding 3.33ml concentration is the toluene solution of the MAO of 1.5M, stirs 2 minutes.Take by weighing 2.93 * 10 -3 G title complex 5 is dissolved in the 5ml toluene solution, and catalyzer is imported in ethene/toluene solution, and polymerization begins.Behind the 20min, reaction terminating, the polymkeric substance suspension liquid is poured in the mixed solution of ethanol and hydrochloric acid, and polyethylene particle is separated out, and uses washing with alcohol, and filtration drying gets the 0.329g polyethylene product.Active 197.4KgPEmol -1H -1Poly molecular weight is 880, and MWD is 1.80.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.

Claims (10)

1. late transition metal complex with formula I structure,
Figure FDA00002037852500011
Wherein, R 1And R 2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R 3Alkyl for hydrogen, halogen or C1 ~ C10;
Mt is Co (II), Fe (II) or Ni (II);
X is a halogen.
2. late transition metal complex according to claim 1 is characterized in that, said R 1And R 2Independently be selected from hydrogen, methyl, ethyl or sec.-propyl separately.
3. late transition metal complex according to claim 1 is characterized in that, said R 3Be hydrogen, halogen, methyl, ethyl or sec.-propyl.
4. late transition metal complex according to claim 1 is characterized in that, said X is Cl or Br.
5. the preparation method of a late transition metal complex may further comprise the steps:
With two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride carry out first set reaction, the part that obtains having the formula II structure in first organic solvent;
The halogenide of said part and rear transition metal is carried out the reaction second time at second organic solvent, and the late transition metal complex that obtains having the formula I structure, said rear transition metal are cobalt, iron or nickel;
Figure FDA00002037852500012
Figure FDA00002037852500021
Wherein, R 1And R 2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R 3Alkyl for hydrogen, halogen or C1 ~ C10;
Mt is Co (II), Fe (II) or Ni (II);
X is a halogen.
6. preparation method according to claim 5 is characterized in that, said two (substituted aniline)-2, and the mol ratio of 6-pyridine diformamide and said phosphorus pentachloride is 1: (1.5 ~ 2.5).
7. a poly preparation method is characterized in that, comprising:
Under the effect of promotor and late transition metal complex with formula I structure, ethene is carried out polyreaction in organic solvent, obtain Vilaterm;
Figure FDA00002037852500022
Wherein, R 1And R 2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R 3Alkyl for hydrogen, halogen or C1 ~ C10;
Mt is Co (II), Fe (II) or Ni (II);
X is a halogen.
8. preparation method according to claim 7 is characterized in that, said promotor is a MAO.
9. preparation method according to claim 7 is characterized in that, said organic solvent is a toluene.
10. preparation method according to claim 7 is characterized in that, the time of said reaction is 0.3 ~ 1h.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1980873A (en) * 2004-07-13 2007-06-13 国际壳牌研究有限公司 Process for preparing linear alpha olefins
CN101302189A (en) * 1996-12-17 2008-11-12 纳幕尔杜邦公司 Novel complexes of pyridinebis(imines) with iron cobalt

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN101302189A (en) * 1996-12-17 2008-11-12 纳幕尔杜邦公司 Novel complexes of pyridinebis(imines) with iron cobalt
CN1980873A (en) * 2004-07-13 2007-06-13 国际壳牌研究有限公司 Process for preparing linear alpha olefins

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
THEO M.SMIT ET AL: "The effect of imine-carbon substituents in bis(imino）pyridine-based ethylene polymerisation catalysts across the transition series", 《CATALYSIS SCIENCE & TECHNOLOGY》 *

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