CN102775448B - Late transition metal complex and its preparation method and preparation method of polyethylene - Google Patents
Late transition metal complex and its preparation method and preparation method of polyethylene Download PDFInfo
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- CN102775448B CN102775448B CN201210299110.3A CN201210299110A CN102775448B CN 102775448 B CN102775448 B CN 102775448B CN 201210299110 A CN201210299110 A CN 201210299110A CN 102775448 B CN102775448 B CN 102775448B
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- -1 polyethylene Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 24
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 24
- 229910052723 transition metal Inorganic materials 0.000 title claims description 82
- 150000003624 transition metals Chemical class 0.000 title claims description 79
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 34
- 230000000694 effects Effects 0.000 claims abstract description 18
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 108
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052736 halogen Inorganic materials 0.000 claims description 23
- 150000002367 halogens Chemical class 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 150000002431 hydrogen Chemical class 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- AIDQCFHFXWPAFG-UHFFFAOYSA-N n-formylformamide Chemical compound O=CNC=O AIDQCFHFXWPAFG-UHFFFAOYSA-N 0.000 claims description 9
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical group [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 29
- 239000005977 Ethylene Substances 0.000 abstract description 15
- 229910001848 post-transition metal Inorganic materials 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000003446 ligand Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 52
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 40
- 239000000047 product Substances 0.000 description 32
- 238000005481 NMR spectroscopy Methods 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 20
- 239000000725 suspension Substances 0.000 description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000001953 recrystallisation Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 229910000071 diazene Inorganic materials 0.000 description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000001448 anilines Chemical class 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- FAYVSPJQASODMO-UHFFFAOYSA-N n-bromo-2,6-dimethylaniline Chemical group CC1=CC=CC(C)=C1NBr FAYVSPJQASODMO-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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
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.Due to features such as rear transition metal have low price, environmental friendliness, the late transition metal catalyst based on olefinic polymerization has been obtained tremendous development 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, and Pd, as central metal, has shown good activity for vinyl polymerization, and utilize this system to realize first the copolymerization of ethene and polar monomer, shown unique polymerization behavior.Nagashima etc. have invented β-diimine NN bidentate system, and it selects Co as central metal, and catalyzed ethylene polymerization has obtained the polyethylene of high molecular.But above-mentioned bidentate System Catalyst structure is relatively unstable, wayward in ethylene polymerization, thereby limit the development of such catalyzer.
Research finds that three toothings are stable, and ligand structure is easily modified, and therefore NNN tridentate pyridine diimine transition metal system catalyzed ethylene polymerization has been subject to extensive concern.At present, the research of NNN tridentate pyridine diimine transition-metal catalyst mainly concentrates on two aspects: 1) by regulating the substituting group on aniline phenyl ring, obtain having the NNN tri-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 object that regulates Polyethylene Chain structure and molecular weight; 2) by changing metal center, obtain the polyethylene of different structure and molecular weight.For example: Gibson etc. are by methoxyl group, and methylthio group is introduced skeleton structure, has synthesized corresponding Fe(II) complex compound, catalyzed ethylene polymerization shows good activity; S.Damavandi etc. introduce nitro in skeleton structure, and catalyzed ethylene polymerization has obtained the polyethylene of high molecular.But when 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,
Wherein, R
1and R
2independently be selected from separately the alkyl of hydrogen or C1 ~ C10;
R
3for the alkyl of hydrogen, halogen or C1 ~ C10;
Mt is Co(II), Fe(II) or Ni(II);
X is halogen.
Preferably, described R
1and R
2independently be selected from separately hydrogen, methyl, ethyl or sec.-propyl.
Preferably, described R
3for hydrogen, halogen, methyl, ethyl or sec.-propyl.
Preferably, described X is Cl or Br.
The present invention also provides a kind of preparation method of late transition metal complex, comprises the following steps:
By two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride carry out first set reaction in the first organic solvent, obtain having the part of formula II structure;
Described part is reacted at the second organic solvent for the second time with the halogenide of rear transition metal, obtain having the late transition metal complex of formula I structure, described rear transition metal is cobalt, iron or nickel;
Wherein, R
1and R
2independently be selected from separately the alkyl of hydrogen or C1 ~ C10;
R
3for the alkyl of hydrogen, halogen or C1 ~ C10;
Mt is Co(II), Fe(II) or Ni(II);
X is halogen.
Preferably, described two (substituted aniline)-2, the mol ratio of 6-pyridine diformamide and described 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:
At promotor and having under the effect of late transition metal complex of formula I structure, ethene is carried out in organic solvent to polyreaction, obtain polyethylene;
Wherein, R
1and R
2independently be selected from separately the alkyl of hydrogen or C1 ~ C10;
R
3for the alkyl of hydrogen, halogen or C1 ~ C10;
Mt is Co(II), Fe(II) or Ni(II);
X is halogen.
Preferably, described promotor is methylaluminoxane.
Preferably, described organic solvent is toluene.
Preferably, the time of described reaction is 0.3 ~ 1h.
The invention provides a kind of late transition metal complex with formula I structure and preparation method thereof, the present invention also provides a kind of poly preparation method, at promotor and having under the effect of late transition metal complex of formula I structure, ethene is carried out in organic solvent to polyreaction, obtain polyethylene.The present invention is incorporated into chlorine atom in pyridine diimine skeleton structure, by thering is part, organic solvent and the rear transition metal halide reaction of formula II structure, rear transition metal element is incorporated into the active centre of pyridine diimine, because 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 title complex skeleton structure become large simultaneously, carry out coordination thereby be conducive to ethene atom, improve the activity of catalyzed ethylene polymerization.Experiment showed, that late transition metal complex is in the process of catalyzed ethylene polymerization, catalytic activity is 300 ~ 1000Kg PEmol
-1h
-1.
Accompanying drawing explanation
Fig. 1 is the crystalline structure figure that the X-single crystal diffraction of the title complex 5 prepared of the embodiment of the present invention 1 characterizes;
Fig. 2 is the crystalline structure figure that the X-single crystal diffraction of the title complex 10 prepared of the embodiment of the present invention 2 characterizes;
Fig. 3 is the crystalline structure figure that the X-single crystal diffraction of the title complex 21 prepared of the embodiment of the present invention 3 characterizes;
Fig. 4 is the crystalline structure figure that the X-single crystal diffraction of the title complex 31 prepared of the embodiment of the present invention 4 characterizes.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The embodiment of the invention discloses a kind of late transition metal complex with formula I structure,
Wherein, R
1and R
2independently be selected from separately the alkyl of hydrogen or C1 ~ C10;
R
3for the alkyl of hydrogen, halogen or C1 ~ C10;
Mt is Co(II), Fe(II) or Ni(II);
X is halogen.
In late transition metal complex provided by the invention, chlorine element has been introduced in pyridine diimine skeleton structure, making Mt-N(C=N) bond distance obviously increases, the positive polarity that proves Mt center active metal has certain increase, carry out coordination thereby be conducive to ethene atom, catalyzed ethylene polymerization has higher activity.
In above-mentioned late transition metal complex, described R
1and R
2for the substituting group on aniline, be independently preferably separately hydrogen, methyl, ethyl or sec.-propyl, more preferably hydrogen, methyl or sec.-propyl.Described R
3be similarly the substituting group on aniline, be preferably hydrogen, halogen or methyl, ethyl or sec.-propyl, more preferably hydrogen, chlorine, bromine or methyl.In above-mentioned late transition metal complex, R
3during for halogen, R
3with X can be same halogen, can be also different halogens, for example R
3during for Cl, X can be Br.
Active atomic centered by described Mt, Mt is rear transition metal, described rear transition metal and early transition metal are to distinguish according to the number of d orbital electron number.Well known to those skilled in the art, described early transition metal is that d layer electronic number is no more than the transition metal of 5, as Sc, V, Ti or Cr etc.; Described rear transition metal is that d layer electronic number exceedes the transition metal of 5, 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, described in there is formula I structure late transition metal complex be specially title complex 1 ~ title complex 40, as shown in table 1, table 1 is for having the concrete title complex table of late transition metal complex of formula I structure,
Table 1 is the concrete title complex table with the late transition metal complex of formula I structure
The present invention also provides the preparation method of late transition metal complex, specifically preparation as follows:
By two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride carry out first set reaction in the first organic solvent, obtain having the part of formula II structure;
Described part is reacted in the second organic solvent for the second time with the halogenide of rear transition metal, obtain having the late transition metal complex of formula I structure, described rear transition metal is cobalt, iron or nickel;
Wherein, R
1and R
1independently be selected from separately the alkyl of hydrogen or C 1 ~ C 10;
R
3for the alkyl of hydrogen, halogen or C 1 ~ C 10;
The process that obtains the part with formula II structure, is specially:
Under nitrogen protection, by two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride, be added in methylene dichloride, and back flow reaction, obtains mix products, by mix products extraction, recrystallization, obtains having the part of formula II structure.
Described two (substituted aniline)-2, the mol ratio of 6-pyridine diformamide and described phosphorus pentachloride is preferably 1:1.5 ~ 2.5, more preferably 1:2, the time of described back flow reaction is preferably 3 ~ 5h, more preferably 3.5 ~ 4.5h.
Obtaining after described part, described part is being reacted in the second organic solvent for the second time with the halogenide of rear transition metal, obtaining having the late transition metal complex of formula I structure.Described the second organic solvent is preferably tetrahydrofuran (THF).The time of described reaction is preferably 3 ~ 7h, more preferably 4 ~ 6h.
According to the present invention, the order that the halogenide of described part, described rear transition metal and described the second organic solvent mix does not limit, and the halogenide of described part, described rear transition metal and described the second organic solvent can be added and reacts simultaneously.Equally also described part can be dissolved in the second organic solvent, the halogenide of described rear transition metal is dissolved in the second organic solvent, then halid the rear transition metal that is dissolved in the second organic solvent solution is dropped in the ligand solution being dissolved in the second organic solvent, react.In order to make the halide reaction of described part and described rear transition metal thorough, the present invention preferably adopts rear kind hybrid mode.
The present invention is incorporated into halogen atom in the skeleton structure of pyridine diimine, by making comparisons with the late transition metal complex with chlorine not, after halogen atom is incorporated into skeleton structure, Mt-N(C=N) bond distance obviously increases, center active metal atom positive polarity is increased, can also make the angle of two phenyl ring in title complex skeleton structure become large, carry out coordination thereby be more conducive to ethene atom, catalyzed ethylene polymerization has higher activity simultaneously.Have in the process of late transition metal complex of formula I structure in preparation, by thering is the halide reaction of part, organic solvent and rear transition metal of formula II structure, rear transition metal element is incorporated into the active centre of pyridine diimine, has obtained described late transition metal complex.
Be applied to and prepare catalyzed ethylene polymerization described late transition metal complex provided by the invention as catalyzer, in polymerization process, catalyzer has shown higher catalytic activity, and the process that the present invention prepares ethene is specially:
Ethene, promotor and the late transition metal complex with formula I structure are carried out to polyreaction in organic solvent, obtain polyethylene;
Wherein, R
1and R
2independently be selected from separately the alkyl of hydrogen or C1 ~ C10;
R
3for the alkyl of hydrogen, halogen or C1 ~ C10;
Mt is Co(II), Fe(II) or Ni(II);
X is halogen.
According to the present invention, described ethene does not limit with the order that described late transition metal complex mixes, and described ethene, organic solvent, promotor and late transition metal complex can be added simultaneously and carries out polyreaction.Equally also can respectively ethene be dissolved in organic solvent, obtain the first solution, promotor is dissolved in organic solvent, obtain the second solution, rear transition metal is dissolved in organic solvent, obtain the 3rd solution, three kinds of solution that obtain are mixed, carry out polyreaction.For described ethene, promotor and late transition metal complex are fully dissolved, the present invention preferably adopts rear kind to add mode.Meanwhile, for polyreaction is abundant, in the process of described polyreaction, preferably guarantee that ethene constantly supplies with.
Described organic solvent is preferably toluene.In above-mentioned polymerization process, if described rear transition metal Individual existence does not have higher activity, need to add promotor, late transition metal complex and described promotor acting in conjunction described in guarantee, thus there is higher catalytic activity.Described promotor is the promotor of catalyzed polyethylene well known to those skilled in the art, and the present invention preferably adopts methylaluminoxane.The time of described polyreaction is preferably 0.3 ~ 1h, more preferably 0.5 ~ 0.8h.Above-mentioned polyreaction was carried out after for some time, preferably polymerization liquid was poured in the mixed solution of ethanol and hydrochloric acid and was stopped polymerization, after filtration, obtained polyethylene.Experiment shows to have the late transition metal complex of formula I structure 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.
By 8.11g(60mmol) 2，4，6-trimethyl aniline and 8.36ml(60mmol) triethylamine is dissolved in 50mlCH
2cl
2in, by 6.1g(30mmol) pyridine dimethyl chloride is dissolved in 20mlCH
2cl
2in, by pyridine dimethyl chloride/CH
2cl
2solution drops to substituted aniline/CH
2cl
2in, reflux after 4 hours, use respectively 100ml water and 100ml1.5M NaCO
3solution washing, adopts separating funnel to obtain the CH of lower floor
2cl
2solution, adds MgSO
4dried overnight, filters and drains, and then carries out recrystallization with toluene, and filtration drying obtains product (5a).Productive rate 91%.Product (5a) is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
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 be prepared.
By product (5a) 5g(12.46mmol) and PCl
55.19g(24.92mmol) in 100ml round-bottomed flask, add afterwards 100ml methylene dichloride, reflux after three hours, drain, adopt hot heptane extraction, obtain lurid n-heptane solution, decompression is evacuated to saturated rear recrystallization, obtains yellow powder product (5b), productive rate 44.6%.Product (5b) is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
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 be prepared.Above-mentioned reaction process is shown below:
By 0.13g(1mmol) CoCl
2be dissolved in 3mlTHF and obtain blue suspension liquid, by part two (2，4，6-trimethyl aniline) pyridine dicarboximide acyl chlorides 0.44g(1mmol) be dissolved in 5ml THF, by part/THF solution at CoCl
2in/THF solution, drip, stir 2h, obtain green suspension, filter to obtain green powder, obtain required title complex.Be dried to obtain 0.4g, productive rate 70.2%.IR（KBr，cm
-1）：1626（v
C=N）。Crystalline structure figure is shown in accompanying drawing 1.Above-mentioned reaction process is as follows:
By 11.94g(60mmol) 4-is bromo-2,6-xylidine and 8.36ml(60mmol) triethylamine is dissolved in 50ml CH
2cl
2in, by 6.1g(30mmol) pyridine dimethyl chloride is dissolved in 20mlCH
2cl
2in, by pyridine dimethyl chloride/CH
2cl
2solution drops to substituted aniline/CH
2cl
2in, reflux after 4 hours, use respectively 100ml water and 100ml 1.5M NaCO
3solution washing, obtains the CH of lower floor with separating funnel
2cl
2solution, adds MgSO
4dried overnight, filters and drains, and then carries out recrystallization with toluene, and filtration drying obtains product (10a), productive rate 86.4%.Product (10a) is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
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 be prepared.
By product (10a) 6.62g(12.46mmol) and PCl
55.19g(24.92mmol) in 100ml round-bottomed flask, add afterwards 100ml methylene dichloride, reflux after three hours, drain, with hot heptane extraction, obtain lurid n-heptane solution, decompression is evacuated to saturated rear recrystallization, obtains yellow powder product (10b), productive rate 44.6%.Product (10b) is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
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 be prepared.Above-mentioned reaction process is as follows:
By 0.13g(1mmol) CoCl
2be dissolved in and in 3mlTHF, obtain blue suspension liquid, by part two (4-bromo-2,6-xylidine) pyridine dicarboximide acyl chlorides 0.57g(1mmol) be dissolved in 5ml THF, part/THF solution is dropped to CoCl
2in/THF solution, stir 2h, obtain green suspension, filter to obtain green powder, obtain required title complex.Be dried to obtain 0.61g, productive rate 87.1%.IR（KBr，cm
-1）：1624（v
C=N）。Crystalline structure figure is shown in accompanying drawing 2.Above-mentioned reaction process is as follows:
By 11.94g(60mmol) 2，4，6-trimethyl aniline and 8.36ml(60mmol) triethylamine is dissolved in 50ml CH
2cl
2in, by 6.1g(30mmol) pyridine dimethyl chloride is dissolved in 20mlCH
2cl
2in, by pyridine dimethyl chloride/CH
2cl
2solution drops to substituted aniline/CH
2cl
2in, reflux after 4 hours, use respectively 100ml water and 100ml 1.5M NaCO
3solution washing, obtains the CH of lower floor with separating funnel
2cl
2solution, adds MgSO
4dried overnight, filters and drains, and then carries out recrystallization with toluene, and filtration drying obtains product (21a), productive rate 86.4%.Product (21a) is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
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 be prepared.
By product (21a) 6.62g(12.46mmol) and PCl
55.19g(24.92mmol) in 100ml round-bottomed flask, add afterwards 100ml methylene dichloride, reflux after three hours, drain, with hot heptane extraction, obtain lurid n-heptane solution, decompression is evacuated to saturated rear recrystallization, obtains yellow powder product (21b), productive rate 44.6%.Product (21b) is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
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 be prepared.Above-mentioned reaction process is as follows:
By 0.13g(1mmol) NiCl
2be dissolved in 3mlTHF and obtain blue suspension liquid, by part two (2，4，6-trimethyl aniline) pyridine dicarboximide acyl chlorides 0.57g(1mmol) be dissolved in 5ml THF, part/THF solution is dropped to NiCl
2in/THF solution, stir 2h, obtain brown suspension, filter to obtain brown ceramic powder, obtain required title complex, be dried to obtain 0.58g, productive rate 86.5%.IR（KBr，cm
-1）:1624（v
C=N）。Crystalline structure figure is shown in accompanying drawing 3.Above-mentioned reaction is as follows:
By 11.94g(60mmol) 2，4，6-trimethyl aniline and 8.36ml(60mmol) triethylamine is dissolved in 50ml CH
2cl
2in, by 6.1g(30mmol) pyridine dimethyl chloride is dissolved in 20ml CH
2cl
2in, by pyridine dimethyl chloride/CH
2cl
2solution drops to substituted aniline/CH
2cl
2in, reflux after 4 hours, use respectively 100ml water and 100ml 1.5M NaCO
3solution washing, obtains the CH of lower floor with separating funnel
2cl
2solution, adds MgSO
4dried overnight, filters and drains, and then carries out recrystallization with toluene, and filtration drying obtains product (31a), productive rate 86.4%.Product (31a) is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
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 be prepared.
By product (31a) 6.62g(12.46mmol) and PCl
55.19g(24.92mmol) in 100ml round-bottomed flask, add afterwards 100ml methylene dichloride, reflux after three hours, drain, with hot heptane extraction, obtain lurid n-heptane solution, decompression is evacuated to saturated rear recrystallization, obtains yellow powder product (31b), productive rate 44.6%.Product (31b) is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
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 be prepared.Above-mentioned reaction process is as follows:
By 0.154g(1mmol) NiBr
2dME is dissolved in 3mlTHF and obtains blue suspension liquid, by part two (2，4，6-trimethyl aniline) pyridine dicarboximide acyl chlorides 0.219g(1mmol) be dissolved in 5ml THF, part/THF solution is dropped to NiBr
2in/THF solution, stir 2h, obtain brown suspension, filter to obtain brown ceramic powder, obtain required title complex, be dried to obtain 0.25g, productive rate 72.6%.IR（KBr，cm
-1）：1624（v
C=N）。Crystalline structure figure is shown in accompanying drawing 4.Above-mentioned reaction process is as follows:
Basic identical with the preparation method of embodiment 1, difference is: by 1mmol FeCl
2be dissolved in 3mlTHF and obtain blue suspension liquid, by part two (2，4，6-trimethyl aniline) pyridine dicarboximide acyl chlorides 0.44g(1mmol) be dissolved in 5ml THF, by part/THF solution at FeCl
2in/THF solution, drip, stir 2h, obtain green suspension, filter to obtain green powder, must there is the title complex 15 of formula II structure.
Basic identical with the preparation method of embodiment 2, difference is: by 1mmol FeCl
2be dissolved in and in 3mlTHF, obtain blue suspension liquid, by part two (4-bromo-2,6-xylidine) pyridine dicarboximide acyl chlorides 0.57g(1mmol) be dissolved in 5ml THF, part/THF solution is dropped to FeCl
2in/THF solution, stir 2h, obtain green suspension, filter to obtain green powder, must there is the title complex 20 of formula III structure.
In 100ml reaction vessel, add 45ml toluene, fill ethene with nitrogen ball, and make toluene solvant unsaturated ethylene, be then placed in 20 ℃ of oil baths, adding 3.33ml concentration is the toluene solution of the methylaluminoxane (MAO) of 1.5M, stirs 2 minutes.Take 2.93 × 10
-3g coordinates 5, is dissolved in 5ml toluene solution, and catalyzer is imported in ethene/toluene solution, and polymerization starts.After 20min, reaction terminating, polymkeric substance suspension liquid is poured in the mixed solution of ethanol and hydrochloric acid, polyethylene Precipitation, by washing with alcohol, filtration drying obtains polyethylene product.Obtain 1.487g.Polymerization activity is 892.2Kg PEmol
-1h
-1.Poly molecular weight is 790, molecular weight distribution 4.23.
In 100ml reaction vessel, add 45ml toluene, fill ethene with nitrogen ball, and make toluene solvant unsaturated ethylene, be then placed in 20 ℃ of oil baths, adding 3.33ml concentration is the toluene solution of the MAO of 1.5M, stirs 2 minutes.Take 3.49 × 10
-3 g title complex 10, is dissolved in 5ml toluene solution, and catalyzer is imported in ethene/toluene solution, and polymerization starts.After 20min, reaction terminating, polymkeric substance suspension liquid is poured in the mixed solution of ethanol and hydrochloric acid, and polyethylene particle is separated out, and by washing with alcohol, filtration drying obtains 0.889g polyethylene product.Activity is 533.4KgPEmol
-1h
-1.Poly molecular weight is 1040, and molecular weight distribution is 2.16.
In 100ml reaction vessel, add 45ml toluene, fill ethene with nitrogen ball, and make toluene solvant unsaturated ethylene, be then placed in 20 ℃ of oil baths, adding 3.33ml concentration is the toluene solution of the MAO of 1.5M, stirs 2 minutes.Take 2.85 × 10
-3 g title complex 15, is dissolved in 5ml toluene solution, and catalyzer is imported in ethene/toluene solution, and polymerization starts.After 20min, reaction terminating, polymkeric substance suspension liquid is poured in the mixed solution of ethanol and hydrochloric acid, and polyethylene particle is separated out, and by washing with alcohol, filtration drying obtains 0.862g polyethylene product.Activity is 517.2KgPEmol
-1h
-1.Poly molecular weight is 980, and molecular weight distribution is 5.72.
In 100ml reaction vessel, add 45ml toluene, fill ethene with nitrogen ball, and make toluene solvant unsaturated ethylene, be then placed in 20 ℃ of oil baths, adding 3.33ml concentration is the toluene solution of the MAO of 1.5M, stirs 2 minutes.Take 3.5 × 10
-3 g title complex 20, is dissolved in 5ml toluene solution, and catalyzer is imported in ethene/toluene solution, and polymerization starts.After 20min, reaction terminating, polymkeric substance suspension liquid is poured in the mixed solution of ethanol and hydrochloric acid, and polyethylene particle is separated out, and by washing with alcohol, filtration drying obtains 1.6608g polyethylene product.Activity is 996.5KgPEmol
-1h
-1.Poly molecular weight is 2370, and molecular weight distribution is 16.45.
In 100ml reaction vessel, add 45ml toluene, fill ethene with nitrogen ball, and make toluene solvant unsaturated ethylene, be then placed in 40 ℃ of oil baths, adding 3.33ml concentration is the toluene solution of the MAO of 1.5M, stirs 2 minutes.Take 2.93 × 10
-3 g title complex 5, is dissolved in 5ml toluene solution, and catalyzer is imported in ethene/toluene solution, and polymerization starts.After 20min, reaction terminating, polymkeric substance suspension liquid is poured in the mixed solution of ethanol and hydrochloric acid, and polyethylene particle is separated out, and by washing with alcohol, filtration drying obtains 1.257g polyethylene product.Activity is 754.6KgPEmol
-1h
-1.Poly molecular weight is 920, and molecular weight distribution is 2.17.
In 100ml reaction vessel, add 45ml toluene, fill ethene with nitrogen ball, and make toluene solvant unsaturated ethylene, be then placed in 60 ℃ of oil baths, adding 3.33ml concentration is the toluene solution of the MAO of 1.5M, stirs 2 minutes.Take 2.93 × 10
-3 g title complex 5, is dissolved in 5ml toluene solution, and catalyzer is imported in ethene/toluene solution, and polymerization starts.After 20min, reaction terminating, polymkeric substance suspension liquid is poured in the mixed solution of ethanol and hydrochloric acid, and polyethylene particle is separated out, and by washing with alcohol, filtration drying obtains 0.329g polyethylene product.Active 197.4KgPEmol
-1h
-1.Poly molecular weight is 880, and molecular weight distribution is 1.80.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles 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 the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.To be apparent for those skilled in the art to the multiple modification of these embodiment, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. one kind has the late transition metal complex of formula I structure;
The preparation method of described late transition metal complex, comprises the following steps:
By two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride carry out first set reaction in the first organic solvent, obtain having the part of formula II structure;
Described part is reacted at the second organic solvent for the second time with the halogenide of rear transition metal, obtain having the late transition metal complex of formula I structure, described rear transition metal is cobalt, iron or nickel;
Wherein, R
1and R
2independently be selected from separately the alkyl of hydrogen or C1～C10;
R
3for the alkyl of hydrogen, halogen or C1～C10;
Mt is Co(II), Fe(II) or Ni(II);
X is halogen.
2. late transition metal complex according to claim 1, is characterized in that, described R
1and R
2independently be selected from separately hydrogen, methyl, ethyl or sec.-propyl.
3. late transition metal complex according to claim 1, is characterized in that, described R
3for hydrogen, halogen, methyl, ethyl or sec.-propyl.
4. late transition metal complex according to claim 1, is characterized in that, described X is Cl or Br.
5. a preparation method for late transition metal complex, comprises the following steps:
By two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride carry out first set reaction in the first organic solvent, obtain having the part of formula II structure;
Described part is reacted at the second organic solvent for the second time with the halogenide of rear transition metal, obtain having the late transition metal complex of formula I structure, described rear transition metal is cobalt, iron or nickel;
Wherein, R
1and R
2independently be selected from separately the alkyl of hydrogen or C1～C10;
R
3for the alkyl of hydrogen, halogen or C1～C10;
Mt is Co(II), Fe(II) or Ni(II);
X is halogen.
6. preparation method according to claim 5, is characterized in that, described two (substituted aniline)-2, the mol ratio of 6-pyridine diformamide and described phosphorus pentachloride is 1:(1.5～2.5).
7. a poly preparation method, is characterized in that, comprising:
At promotor and having under the effect of late transition metal complex of formula I structure, ethene is carried out in organic solvent to polyreaction, obtain polyethylene;
The preparation method of described late transition metal complex, comprises the following steps:
By two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride carry out first set reaction in the first organic solvent, obtain having the part of formula II structure;
Described part is reacted at the second organic solvent for the second time with the halogenide of rear transition metal, obtain having the late transition metal complex of formula I structure, described rear transition metal is cobalt, iron or nickel;
Wherein, R
1and R
2independently be selected from separately the alkyl of hydrogen or C1～C10;
R
3for the alkyl of hydrogen, halogen or C1～C10;
Mt is Co(II), Fe(II) or Ni(II);
X is halogen.
8. preparation method according to claim 7, is characterized in that, described promotor is methylaluminoxane.
9. preparation method according to claim 7, is characterized in that, described organic solvent is toluene.
10. preparation method according to claim 7, is characterized in that, the time of described polyreaction is 0.3～1h.
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