CN102775539B - Preparation method of polybutadiene - Google Patents
Preparation method of polybutadiene Download PDFInfo
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- CN102775539B CN102775539B CN201210299125.XA CN201210299125A CN102775539B CN 102775539 B CN102775539 B CN 102775539B CN 201210299125 A CN201210299125 A CN 201210299125A CN 102775539 B CN102775539 B CN 102775539B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 11
- 239000005062 Polybutadiene Substances 0.000 title claims abstract 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 40
- 150000004700 cobalt complex Chemical class 0.000 claims abstract description 33
- 239000003960 organic solvent Substances 0.000 claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- -1 methylaluminum alkoxide Chemical class 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 47
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 21
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 15
- 239000004411 aluminium Substances 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000003708 ampul Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 239000003292 glue Substances 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 150000001868 cobalt Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- AIDQCFHFXWPAFG-UHFFFAOYSA-N n-formylformamide Chemical compound O=CNC=O AIDQCFHFXWPAFG-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 150000001448 anilines Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 150000004753 Schiff bases Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 201000011180 Dental Pulp Calcification Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- MGYYPGVDFNPEJL-UHFFFAOYSA-N N-chloro-2,6-dimethylaniline Chemical group CC1=CC=CC(C)=C1NCl MGYYPGVDFNPEJL-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a preparation method of a polybutadiene, which comprises the following steps: under the actions of a cocatalyst and a cobalt complex disclosed as Formula (I), carrying out polymerization reaction on butadiene in an organic solvent to obtain polybutadiene. In the polybutadiene preparation process, the cobalt complex disclosed as Formula (I) and the cocatalyst are used as the catalyst, the electrophilic chlorine atoms introduced into the ligand structure of the cobalt complex increase the electropositivity of the active center cobalt atom, thereby endowing the butadiene monomer with larger coordination space; and thus, the cobalt complex has higher catalytic activity, so the polybutadiene has higher yield. The experiment proves that the yield of polybutadiene is 72-97% in the butadiene catalytic polymerization process of the cobalt complex.
Description
Technical field
The present invention relates to technical field of polymer, relate in particular to a kind of preparation method of polyhutadiene.
Background technology
Synthetic rubber is a kind of very important synthetic materials, has application extremely widely in the fields such as automobile, building, medical treatment.Along with the development of China Synthetic Rubber Industry, polybutadiene rubber, owing to having the advantages such as good springiness, wear resistance is strong, heat-dissipating is low, hysteresis loss is little, is widely used in the production of the rubber items such as tire, adhesive tape, sebific duct and rubber overshoes.Polybutadiene rubber is to take a kind of general purpose synthetic rubber that 1,3-butadiene obtains as monomer polymerization.
Up to now, the catalyst system that in prior art, Butadiene Polymerization is conventional has LiR, TiCl
4/ I
2/ Al
ibu
3, Co(OCOR)
2/ H
2o/AlEt
2cl, Ni(OCOR)
2/ BF
3oEt
2/ AlEt
3, Nd(OCOR)
3/ Et
3al
2cl
3/ Al
ibu
2h, above-mentioned five catalyst systems have successfully been realized the industrialization of polymerizing butadiene.Wherein, cobalt series catalyst is as one of industrialized five large catalyzer, and its Butadiene Polymerization has distinct stereoselective, in the situation that different part and give electronics can obtain cis-1, two kinds of Langmuir-Blodgett Films of 4-and 1,2-.For example, cobalt salt directly under alkylaluminium cpd effect catalysis obtain high-cis-1，4-polybutadiene; And when introducing the electron donors such as triphenylphosphine or dithiocarbonic anhydride in polymerization system, be conducive to obtain 1, the polyhutadiene of 2-structure.In view of cobalt series catalyst adopts different promotors, can obtain the polyhutadiene of different structure, in industrial production, often adopt cobalt series catalyst Butadiene Polymerization.
The cobalt series catalyst of Schiff bases part becomes the focus of research, and this type of catalyzer has single active centre, and Butadiene Polymerization also has good selectivity.For example, pyridine list imines alcohols NNO tri-denticle systems, the Butadiene Polymerizations such as salicylic alidehyde imine NO bidentate system have good activity, can access the polyhutadiene of high-cis.But during the cobalt series catalyst Butadiene alkene polymerization of existing Schiff bases part, catalytic activity is still lower, thereby makes the yield of polyhutadiene lower.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method with the polyhutadiene of higher yields.
In view of this, the invention provides a kind of preparation method of polyhutadiene, comprising:
At promotor with have under the effect of cobalt complex of formula I structure, divinyl is carried out in organic solvent to polyreaction, obtain polyhutadiene;
Wherein, R
1and R
2independently be selected from separately the alkyl of hydrogen or C1 ~ C10;
R
3alkyl for hydrogen, halogen or C1 ~ C10;
X is halogen.
Preferably, the mol ratio of described cobalt complex and described divinyl is 1:(1000 ~ 5000).
Preferably, the temperature of described polyreaction is 0 ~ 100 ℃.
Preferably, described promotor is diethyl sesquialter aluminium, triisobutyl aluminium, triethyl aluminum or methyl alcoxyl aluminium.
Preferably, the time of described polyreaction is 0.05h ~ 4h.
Preferably, described R
1and R
2independently be selected from separately hydrogen, methyl, ethyl or sec.-propyl.
Preferably, described R
3for hydrogen, chlorine, bromine, methyl, ethyl or sec.-propyl.
Preferably, the preparation method of described cobalt complex is specially:
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 cobalt, obtain having the cobalt complex of formula I structure;
Wherein, R
1and R
2independently be selected from separately the alkyl of hydrogen or C1 ~ C10;
R
3alkyl for hydrogen, halogen or C1 ~ C10;
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).
Preferably, the time of described first set reaction is 3 ~ 5h, and the described time of reaction is for the second time 3 ~ 7h.
The invention provides a kind of preparation method of polyhutadiene, at promotor with have under the effect of cobalt complex of formula I structure, divinyl is carried out in organic solvent to polyreaction, obtain polyhutadiene.The present invention is in preparing the process of polyhutadiene, adopted and there is the cobalt complex of formula I structure and promotor as catalyzer, owing to having introduced electrophilic chlorine atom in the ligand structure of cobalt complex, increased the positive polarity of active centre cobalt atom, make the angle of two phenyl ring become large, thereby reduced active centre cobalt steric hindrance around, given divinylic monomer larger Coordination Space, make catalyzer there is higher catalytic activity, so polyhutadiene have higher yield.Experiment showed, that cobalt complex is in the process of Butadiene Polymerization, the yield of polyhutadiene is 72% ~ 97%.
Accompanying drawing explanation
Fig. 1 is the crystalline structure figure that the X-single crystal diffraction of the title complex 5 of the embodiment of the present invention 1 preparation characterizes;
Fig. 2 is the crystalline structure figure that the X-single crystal diffraction of the title complex 9 of the embodiment of the present invention 2 preparations characterizes;
The crystalline structure figure that the X-single crystal diffraction of the title complex 10 of Fig. 3 embodiment of the present invention 3 preparations characterizes;
Fig. 4 is the active comparative graph of title complex 5 and title complex 31 Butadiene Polymerizations.
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 preparation method who the embodiment of the invention discloses a kind of polyhutadiene, is specially:
At promotor with have under the effect of cobalt complex of formula I structure, divinyl is carried out in organic solvent to polyreaction, obtain polyhutadiene;
Wherein, R
1and R
2independently be selected from separately the alkyl of hydrogen or C1 ~ C10;
R
3alkyl for hydrogen, halogen or C1 ~ C10;
X is halogen.
In above-mentioned polymerization process, the independent Butadiene Polymerization of described cobalt complex, has catalytic activity, but adds after promotor, cobalt complex and promotor co-catalysis polymerizing butadiene, and catalyzer has higher catalytic activity.Described promotor is preferably diethyl sesquialter aluminium, triisobutyl aluminium, triethyl aluminum or methyl alcoxyl aluminium, more preferably diethyl sesquialter aluminium.In aluminium in described promotor and described cobalt complex, the mol ratio of cobalt is preferably 50 ~ 100.
In above-mentioned cobalt 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, 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, as, R
3during for Cl, X can be Br.Cobalt is a kind of rear transition metal, and it is as the active centre atom of title complex, and 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 surpasses the transition metal of 5.
According to the present invention, described in there is formula I structure cobalt complex be specially title complex 1 ~ title complex 30, as shown in table 1, table 1 is for having the concrete title complex table of the late transition metal complex of formula I structure,
Table 1 is for having the concrete title complex table of the late transition metal complex of formula I structure
According to the present invention, described in there is the preparation method of the cobalt complex of formula II structure, 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 cobalt, obtain having the cobalt complex of formula I structure;
Wherein, R
1and R
2independently be selected from separately the alkyl of hydrogen or C1 ~ C10;
R
3alkyl for hydrogen, halogen or C1 ~ C10;
X is halogen.
The described preparation process with the part of 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 ~ 2.5,1:2 more preferably, the time of described back flow reaction is preferably 3 ~ 5h, more preferably 3.5 ~ 4.5h.
After obtaining described part, described part is reacted in the second organic solvent for the second time with the halogenide of cobalt, obtain having the cobalt 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 not restriction of order that the halogenide of described part, described cobalt and described the second organic solvent mix, can add the halogenide of described part, described cobalt and described the second organic solvent to react simultaneously.Equally also described part can be dissolved in the second organic solvent, the halogenide of described cobalt is dissolved in the second organic solvent, then the halide solution that is dissolved in the cobalt of the second organic solvent be 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 cobalt thorough, the present invention preferably adopts rear kind hybrid mode.
After prepared by the cobalt complex with formula I structure, the present invention, using the cobalt complex with formula I structure as catalyzer, carries out divinyl polyreaction in organic solvent.In carrying out the process of polyreaction, the order that described divinyl mixes with described cobalt complex is restriction not, described divinyl, organic solvent, promotor and cobalt complex can be added simultaneously and carries out polyreaction.Equally also can respectively divinyl be dissolved in organic solvent, obtain the first solution, promotor is dissolved in organic solvent, obtain the second solution, the title complex of cobalt is dissolved in organic solvent, obtain the 3rd solution; Then three kinds of solution that obtain are mixed, carry out polyreaction.For described divinyl, promotor and cobalt 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.The temperature of described polyreaction is preferably 0 ~ 80 ℃, more preferably 20 ~ 60 ℃.The time that described polyreaction is is preferably 0.05h ~ 4h, and more preferably 0.1 ~ 2h, most preferably is 0.3 ~ 1h.
Described in the present invention, organic solvent is preferably toluene.The volume of described organic solvent is 15 ~ 20mL.The mol ratio of described cobalt complex and described divinyl is preferably 1:(1000 ~ 5000), 1:(2000 ~ 4000 more preferably), most preferably be 1:3000.Test shows to have the cobalt complex of formula I structure in the process of Butadiene Polymerization, and the yield of the polyhutadiene obtaining is 72 ~ 97%.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of polyhutadiene provided by the invention is elaborated, protection scope of the present invention is not limited by the following examples.
Reagent in the embodiment of the present invention is commercially available prod.
Embodiment 1
Take 5g(30mmol) pyridine-2,6-dioctyl phthalate, to 50mL round-bottomed flask, adds 30mL sulfur oxychloride, and backflow 24h is to forming homogeneous phase, and the sulfur oxychloride that decompressing and extracting is unnecessary obtains the pyridine dimethyl chloride of pale pink, directly as next step reaction.
Take 8.11g(60mmol) 2，4，6-trimethyl aniline and 8.36g(60mmol) triethylamine is dissolved in 50ml CH
2cl
2in, taking 6.1g(30mmol) pyridine dimethyl chloride is dissolved in 20mL CH
2cl
2in, pyridine dimethyl chloride/CH
2cl
2solution is toward substituted aniline/CH
2cl
2middle dropping, refluxed after 4 hours, used respectively 100ml water and 100ml1.5M Na
2cO
3solution washing, obtains the CH of lower floor with separating funnel
2cl
2solution, adds MgSO
4dried overnight, filters and drains, and then with toluene, carries out recrystallization, and filtration drying obtains product (5b), and productive rate is 91%.Product (5b) 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 (5b) can be prepared.
Take 5g(12.46mmol) (5b) and 5.19g(24.92mmol) PCl
5in 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 (5c), and productive rate is 44.6%.Product (5c) 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 part (5c) can be prepared.Above-mentioned reaction process is as follows:
Take 0.13g(1mmol) CoCl
2being dissolved in 3mL THF and obtaining blue suspension liquid, take 0.44g(1mmol) part (5c) is dissolved in 5mL THF, and part/THF solution is toward 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）。Above-mentioned reaction process is as follows:
Embodiment 2
Take 5g(30mmol) dinicotinic acid to 50mL round-bottomed flask, add 30mL sulfur oxychloride, backflow 24h is to forming homogeneous phase, the sulfur oxychloride that decompressing and extracting is unnecessary obtains the pyridine dimethyl chloride of pale pink, directly as next step reaction.
Take 9.3g(60mmol) 4-is chloro-2,6-xylidine and 8.36ml(60mmol) triethylamine is dissolved in 50mL CH
2cl
2in, taking 6.1g(30mmol) pyridine dimethyl chloride is dissolved in 20mLCH
2cl
2in, pyridine dimethyl chloride/CH
2cl
2solution is toward substituted aniline/CH
2cl
2middle dropping, refluxed after 4 hours, used respectively 100mL water and 100mL1.5M Na
2cO
3solution washing, obtains the CH of lower floor with separating funnel
2cl
2solution, adds MgSO
4dried overnight, filters and drains, and then with toluene, carries out recrystallization, and filtration drying obtains product (9b).Productive rate 83.5%.Product (9b) 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), 8.54(d, 2H, Pyr-H
m), 8.19(t, 1H, Pyr-H
o), 7.16(s, 4H, Ar-H), 2.28(s, 12H ,-CH
3).
13C?NMR（100MHz，CDCl
3，δ，ppm）：161.5，148.6，139.5，137.1，132.8，131.8，128.1，125.8，18.4。Hence one can see that, and product (9b) can be prepared.
Take (9b) 5.51g(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 (9c), productive rate 63%.Product (9c) is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR(400MHz, CDCl
3, δ, ppm): 8.50(d, 2H, Pyr-H
m), 8.03(t, 1H, Pyr-H
o), 7.11(s, 4H, Ar-H), 2.11(s, 12H ,-CH
3).
13C?NMR（100MHz，CDCl
3，δ，ppm）：150.8，145.2，144.1，137.6，129.4，127.8，127.7，125.6，17.6。IR（KBr，cm
-1）：1656（v
C=N）。Hence one can see that, and part (9c) can be prepared.Above-mentioned reaction process is as follows:
Take 0.13g(1mmol) CoCl
2being dissolved in 3mL THF and obtaining blue suspension liquid, take 0.48g(1mmol) part (9c) is dissolved in 5mL THF, and part/THF solution is toward CoCl
2in/THF solution, drip, stir 2h, obtain green suspension, filter to obtain green powder, obtain required title complex.Be dried to obtain 0.53g, productive rate 86.9%.IR（KBr，cm
-1）：1625（v
C=N）。Above-mentioned reaction process is as follows:
Embodiment 3
Take 5g(30mmol) dinicotinic acid to 50mL round-bottomed flask, add 30mL sulfur oxychloride, backflow 24h is to forming homogeneous phase, the sulfur oxychloride that decompressing and extracting is unnecessary obtains the pyridine dimethyl chloride of pale pink, directly as next step reaction.
Take 11.94g(60mmol) 4-is bromo-2,6-xylidine and 8.36mL(60mmol) triethylamine is dissolved in 50mL CH
2cl
2in, taking 6.1g(30mmol) pyridine dimethyl chloride is dissolved in 20mL CH
2cl
2in, pyridine dimethyl chloride/CH
2cl
2solution is toward substituted aniline/CH
2cl
2middle dropping, refluxed after 4 hours, used respectively 100mL water and 100mL1.5M Na
2cO
3solution washing, obtains the CH of lower floor with separating funnel
2cl
2solution, adds MgSO
4dried overnight, filters and drains, and then with toluene, carries out recrystallization, and filtration drying obtains product (10b).Productive rate 86.4%.Product (10b) 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 (10b) can be prepared.
Take (10b) 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 (10c), productive rate 44.6%.Product (10c) 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 part (10c) can be prepared.Above-mentioned reaction process is as follows:
Take 0.13g(1mmol) CoCl
2being dissolved in 3mL THF and obtaining blue suspension liquid, take 0.57g(1mmol) part (10c) is dissolved in 5mL THF, and part/THF solution is toward CoCl
2in/THF solution, drip, 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）。Above-mentioned reaction process is as follows:
Embodiment 4
Basic identical with the preparation method of embodiment 1, difference is: 60mmol aniline and 60mmol triethylamine are dissolved in to 50mLCH
2cl
2in, all the other operation stepss are identical, obtain having the title complex 1 of formula III structure.
Embodiment 5
Divinylic monomer is passed in toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In the previously baked ampoule filling after nitrogen, take 0.006g title complex 1, then add 20mL divinyl toluene solution, shake up, with syringe, add 0.5mL diethyl sesquialter aluminium, become homogeneous phase solution, put into the water bath with thermostatic control initiated polymerization of pre-prepd 20 ℃, after 20min, to adding in polymerization bottle, contain 2, the ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and a small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out a large amount of washing with alcohol of glue, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 71.8%, and molecular weight is 17.54 * 10
4, molecular weight distribution is 2.77, cis-1,4 content is 96%.
Embodiment 6
Divinylic monomer is passed in toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In the previously baked ampoule filling after nitrogen, take 0.0075g title complex 9, then add 20mL divinyl toluene solution, shake up, with syringe, add 0.5mL diethyl sesquialter aluminium, become homogeneous phase solution, put into the water bath with thermostatic control initiated polymerization of pre-prepd 20 ℃, after 20min, to adding in polymerization bottle, contain 2, the ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and a small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out a large amount of washing with alcohol of glue, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 93.6%, and molecular weight is 6.48 * 10
4.Molecular weight distribution is 4.82, cis-1, and the content of 4-is 94.4%.
Embodiment 7
Divinylic monomer is passed in toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In the previously baked ampoule filling after nitrogen, take 0.007g title complex 5, then add 20mL divinyl toluene solution, shake up, with syringe, add 1mL diethyl sesquialter aluminium, become homogeneous phase solution, put into the water bath with thermostatic control initiated polymerization of pre-prepd 20 ℃, after 3min, to adding in polymerization bottle, contain 2, the ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and a small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out a large amount of washing with alcohol of glue, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 74%, and molecular weight is 7.03 * 10
4, molecular weight distribution is 1.62, cis-1, the content of 4-is 97.7%.
Embodiment 8
Divinylic monomer is passed in toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In the previously baked ampoule filling after nitrogen, take 0.007g title complex 5, then add 20mL divinyl toluene solution, shake up, with syringe, add 1mL diethyl sesquialter aluminium, become homogeneous phase solution, put into the water bath with thermostatic control initiated polymerization of pre-prepd 20 ℃, after 8min, to adding in polymerization bottle, contain 2, the ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and a small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out a large amount of washing with alcohol of glue, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 76.2%, and molecular weight is 7.05 * 10
4, molecular weight distribution is 3.46, cis-1, the content of 4-is 93%.
Divinylic monomer is passed in toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In the previously baked ampoule filling after nitrogen, take 0.007g title complex 5, then add 20mL divinyl toluene solution, shake up, with syringe, add 0.5mL diethyl sesquialter aluminium, become homogeneous phase solution, put into the water bath with thermostatic control initiated polymerization of pre-prepd 0 ℃, after 20min, to adding in polymerization bottle, contain 2, the ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and a small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out a large amount of washing with alcohol of glue, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 74.7%, and molecular weight is 18.0 * 10
4, molecular weight distribution is 1.81, cis-1, the content of 4-is 98.5%.
Embodiment 10
Divinylic monomer is passed in toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In the previously baked ampoule filling after nitrogen, take 0.007g title complex 5, then add 20mL divinyl toluene solution, shake up, with syringe, add 0.5mL diethyl sesquialter aluminium, become homogeneous phase solution, put into the water bath with thermostatic control initiated polymerization of pre-prepd 80 ℃, after 20min, to adding in polymerization bottle, contain 2, the ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and a small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out a large amount of washing with alcohol of glue, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 70%, and molecular weight is 2.14 * 10
4, molecular weight distribution is 7.53, cis-1, the content of 4-is 76.8%.
Embodiment 11
Divinylic monomer is passed in toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In the previously baked ampoule filling after nitrogen, take 0.007g title complex 5, then add 20mL divinyl toluene solution, shake up, with syringe, add 0.05mL methylaluminoxane, become homogeneous phase solution, put into the water bath with thermostatic control initiated polymerization of pre-prepd 20 ℃, after 4h, to adding in polymerization bottle, contain 2, the ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and a small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out a large amount of washing with alcohol of glue, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 73.5%, and molecular weight is 0.81 * 10
4molecular weight distribution is 3.72, cis-1, and the content of 4-is 94.9.
Divinylic monomer is passed in toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In the previously baked ampoule filling after nitrogen, take 0.007g title complex 5, then add 20mL divinyl toluene solution, shake up, with syringe, add 0.5mL diethyl sesquialter aluminium, become homogeneous phase solution, put into the water bath with thermostatic control initiated polymerization of pre-prepd 20 ℃, after 20min, to adding in polymerization bottle, contain 2, the ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and a small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out a large amount of washing with alcohol of glue, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 97%, and molecular weight is 5.32 * 10
4, molecular weight distribution is 5.19, cis-1, the content of 4-is 93.1%.Fig. 4 is title complex 5 and the polymerization activity graphic representation of title complex 31 under different time, and in figure, ■ curve is the polymerization activity curve of polymkeric substance 5.
Embodiment 13
Divinylic monomer is passed in toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In the previously baked ampoule filling after nitrogen, take 0.007g title complex 5, then add 20mL divinyl toluene solution, shake up, with syringe, add 0.5mL diethyl sesquialter aluminium, become homogeneous phase solution, put into the water bath with thermostatic control initiated polymerization of pre-prepd 20 ℃, after 8min, to adding in polymerization bottle, contain 2, the ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and a small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out a large amount of washing with alcohol of glue, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 76.2%, and molecular weight is 7.0 * 10
4, molecular weight distribution is 3.46, cis-1, the content of 4-is 93.0.Fig. 4 is title complex 5 and the polymerization activity graphic representation of title complex 31 under different time, and in figure, ■ curve is the polymerization activity curve of polymkeric substance 5.As shown in Figure 4, polymkeric substance 5 has higher catalytic activity.
Comparative example 1
Divinylic monomer is passed in toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In the previously baked ampoule filling after nitrogen, take the title complex 31 that 0.0065g has formula IV structure, then add 20mL divinyl toluene solution, shake up, with syringe, add 0.5mL diethyl sesquialter aluminium, become homogeneous phase solution, put into the water bath with thermostatic control initiated polymerization of pre-prepd 20 ℃, after 20min, to adding in polymerization bottle, contain 2, the ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and a small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out a large amount of washing with alcohol of glue, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 92%, and molecular weight is 5.32 * 10
4, molecular weight distribution is 5.21, cis-1, the content of 4-is 93.1%.Fig. 4 is title complex 5 and the polymerization activity graphic representation of title complex 31 under different time, in figure ● curve is the polymerization activity curve of polymkeric substance 31.
Comparative example 2
Divinylic monomer is passed in toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.Bottled nitrogen ampoule after pre-baking, the weighed 0.0065g complexes 31 and then added to 20mL of butadiene in toluene, shaken with diethyl syringe was added 0.5mL sesquichloride, homogeneous solution, put prepared into a thermostatic bath at 20 ℃ to initiate polymerization, 8min, the vial was added to the polymerization comprising 2,6 - di-tert-butyl-4 - methylphenol (1wt/v-%) and a small amount of hydrochloric acid (2v / v -%) of ethanol to terminate the polymerization reaction, the precipitate was washed with ethanol and a large number of plastic, 40 ℃ constant temperature and dried to constant weight.The yield of polyhutadiene is 32.3%, and molecular weight is 10.4 * 10
4, molecular weight distribution is 2.1, cis-1, the content of 4-is 95.9%.Fig. 4 is title complex 5 and the polymerization activity graphic representation of title complex 31 under different time, in figure ● curve is the polymerization activity curve of polymkeric substance 31.
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.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, 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)
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