CN108659036A - A kind of vanadium complex, preparation method and the application in isoprene polymerization - Google Patents
A kind of vanadium complex, preparation method and the application in isoprene polymerization Download PDFInfo
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- CN108659036A CN108659036A CN201810402184.2A CN201810402184A CN108659036A CN 108659036 A CN108659036 A CN 108659036A CN 201810402184 A CN201810402184 A CN 201810402184A CN 108659036 A CN108659036 A CN 108659036A
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- isoprene
- vanadium
- complex
- tetrahydrofuran
- catalyst
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 36
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 36
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003446 ligand Substances 0.000 claims abstract description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003426 co-catalyst Substances 0.000 claims abstract description 12
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 10
- 239000012312 sodium hydride Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 8
- 150000004820 halides Chemical class 0.000 claims abstract description 7
- 238000012805 post-processing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 229920001195 polyisoprene Polymers 0.000 claims description 14
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 229960005222 phenazone Drugs 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- -1 butyl aluminium Chemical compound 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 21
- 229920003049 isoprene rubber Polymers 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 150000003681 vanadium Chemical class 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000029936 alkylation Effects 0.000 abstract 1
- 238000005804 alkylation reaction Methods 0.000 abstract 1
- 150000001638 boron Chemical class 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 18
- 229910052748 manganese Inorganic materials 0.000 description 15
- 238000001914 filtration Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000010183 spectrum analysis Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 2
- TWDJIKFUVRYBJF-UHFFFAOYSA-N Cyanthoate Chemical compound CCOP(=O)(OCC)SCC(=O)NC(C)(C)C#N TWDJIKFUVRYBJF-UHFFFAOYSA-N 0.000 description 1
- 239000000899 Gutta-Percha Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 240000000342 Palaquium gutta Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- AZLYZRGJCVQKKK-UHFFFAOYSA-N dioxohydrazine Chemical compound O=NN=O AZLYZRGJCVQKKK-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920000588 gutta-percha Polymers 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/005—Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention provides a kind of vanadium complex, preparation method and the application in isoprene polymerization, is related to the technical field of high molecular material preparation, specifically, belongs to poly- isoprene rubber synthesis field.For solve complex catalysis isoprene polymerization polymer architecture selectivity it is not high, vanadium series catalyst is active low the problems such as, vanudium complex provided by the invention is reacted tridentate ligand with sodium hydride by room temperature in tetrahydrofuran is prepared into sodium salt；Then sodium salt reacts in tetrahydrofuran with the halide of vanadium, is obtained after post-processing.Isoprene in organic solvent, reacts the isoprene rubber based on obtained cis- Isosorbide-5-Nitrae under the vanudium complex and co-catalyst effect.Vanudium complex preparation method of the present invention is simple, and application of the vanadium metal in olefinic polyreaction is effectively expanded compared to using the polymerisation of boron salt class alkylation removal reagent more cheap and easy to get to temperature-insensitive, has industrial value well.
Description
Technical field
The present invention relates to technical fields prepared by high molecular material, specifically, belong to poly- isoprene rubber synthesis field.
Background technology
Isoprene rubber is a kind of rubber being polymerize under the action of catalyst by isoprene monomer, also known as synthesizes day
T PNR is widely used in people's lives, such as tire, medical material and golf ball, academic research with
And extensive concern is all obtained in industrial production.From structure, polyisoprene can be divided into 1,2- isoprene rubbers, 3,4- isoamyl rubbers
Glue, anti-form-1,4- isoprene rubbers and cis- -1,4- isoprene rubbers.The performance that the isoprene rubber of different structure is shown has very
Big difference.For example, cis--Isosorbide-5-Nitrae-isoprene rubber in structure and performance closer to natural rubber, be widely used in tire,
The rubber processings such as sebific duct；Anti-form-1,4- isoprene rubber performances are more closely similar to gutta-percha, have excellent dynamic mechanical
With good wear-resisting property；3,4- isoprene rubbers have good wet skid energy hysteresis loss low with high temperature, are a kind of low lifes
The tartan of heat, high wet-sliding resistant.Currently, having the catalytic polymerization of numerous studies report isoprene, urged by regulation and control
Agent, co-catalysis reaction condition obtain the isoprene rubber of different structure.Catalyst plays heavy to closing in isoprene polymerization
The effect wanted is the core content in isoprene rubber preparation research.The transition metal-catalyzed main collection of isoprene polymerization research
In in Section III and Group IV, wherein industrially mainly synthesizing isoprene rubber, cis- Isosorbide-5-Nitrae-using titanium system and rare earth series catalysts
Structure is up to 98%.In addition, late transition metal catalyst is also widely studied in isoprene polymerization, as iron and cobalt are matched
Close object.However, the application study and few for transition metal in isoprene rubber preparation.Wherein vanadium series catalyst early in
Nineteen fifty is applied in olefinic polyreaction, is earliest one of homogeneous polymerization reaction system.The heterogeneous system of vanadium catalysis
In, VCl3、VCl4、VOCl3、V(acac)3And VCl33THF is catalyzed isoprene under the collective effect of aluminum alkyl catalyst
Polymerization can obtain anti-form-1,4 structure isoprene rubbers.But since vanadium series catalyst is easy to be reduced in these systems
Low price object and make catalyst inactivation, and then cause the above system catalytic efficiency relatively low.The method for solving catalyst inactivation mainly has
It is two kinds, another then be that ligand is introduced on vanadium metal come in further stablizing one is being added oxidant in catalyst system and catalyzing
Heart metal.Zinck seminars report V [ONNO] complex-catalyzed isoprene polymerization, and catalytic activity is higher, but poly- isoamyl
The molecular weight of diene is relatively low, and the selectivity of the polymerisation is not high, 3,4 structures and cis--Isosorbide-5-Nitrae structure in polyisoprene
Ratio be 68/32.Therefore, explore high activity, highly-solid selectively vanadium series catalyst come realize isoprene it is controllable gather
Synthesize a challenge of academia.
Invention content
Purpose of the present invention is on the basis of existing technology, provide a kind of new vanadium complex and preparation method thereof, simultaneously
It has further related to be applied to the catalyst in the polymerisation of isoprene, has obtained high-cis-Isosorbide-5-Nitrae, high molecular weight and narrow point
The polyisoprene of son amount distribution.
To achieve the goals above, the present invention provides a kind of vanadium complex, the structural formula such as Formulas I institutes of the vanadium complex
Show.
Ligand is added to the tetrahydrofuran solution of sodium hydride at -30 DEG C, risen to by the preparation method of the vanadium complex
Room temperature reaction 4 hours, at room temperature by above-mentioned clarified solution be transferred to equimolar than VCl3(THF)3Tetrahydrofuran solution in it is anti-
It answers, after reaction post-treated drying to constant weight.
The present invention is achieved by the following technical solutions：
The present invention provides a kind of vanadium complex.The vanadium complex has structure shown in Formulas I：
Wherein, R1For in methyl, ethyl or phenyl one kind or two kinds or three kinds, R2For hydrogen-based or tertiary butyl；Its structural formula
For the one or two or more kinds in following structural formula：
The present invention also provides the preparation methods of the vanudium complex, specially：(1) at room temperature, by tridentate ligand and hydrogen
Change sodium reacts in tetrahydrofuran is prepared into sodium salt；(2) and then sodium salt reacts in tetrahydrofuran with the halide of vanadium, post-processing
After obtain vanudium complex.
The preparation method of above-mentioned vanudium complex, step (1) described tridentate ligand are added to the tetrahydrochysene of sodium hydride at -30 DEG C
Tetrahydrofuran solution is warmed to room temperature is reacted later, and the molar ratio of the tridentate ligand and sodium hydride is 1:1, the reaction time is 4 small
When；A concentration of 0.2-0.6mol/L of the sodium hydride in tetrahydrofuran；The tridentate ligand structural formula is in following structural formula
It is one or two or more kinds of：
The molar ratio of the halide of the preparation method of above-mentioned vanudium complex, step (2) sodium salt and vanadium is 1:1, it is described
Reaction time is 4-8 hours；A concentration of 0.2-0.6mol/L of the halide of the vanadium in tetrahydrofuran.
The present invention also provides application of the vanadium complex in being catalyzed isoprene polymerization, and the application, which is included in, to be had
The polyisoprene based on cis- -1,4 is made in solvent and the lower reaction of above-mentioned catalyst and co-catalyst effect.Specially：
The vanudium complex, organic solvent, monomer isoprene, co-catalyst are sequentially added in the reaction vessel, or are sequentially added
The vanudium complex, organic solvent, co-catalyst, monomer isoprene；Heating carries out polymerisation, through post-processing after reaction
To the product of predominantly cis- -1,4- polyisoprene.
The application, preferably charging sequence are：After vanadium complex and organic solvent are separately added into, isoamyl two is sequentially added
Alkene and co-catalyst.The molar ratio of monomer isoprene and vanadium complex is (1000-5000):1；Organic solvent and monomer isoamyl
The volume ratio of diene is (1-10):1.The organic solvent is toluene, paraxylene, n-hexane, hexamethylene, pentane, positive heptan
One or two or more kinds in alkane, tetrahydrofuran or dichloromethane, preferably toluene.The co-catalyst is trimethyl aluminium, three second
One or two or more kinds in base aluminium, triisobutyl aluminium, methylaluminoxane or the methylaluminoxane of modification；Methylaluminoxane
(MAO) general structure isWherein n is the natural number of 4-40；In aluminium element and vanadium complex in co-catalyst
The molar ratio of v element is (100-1000):1.
The application, preferably isoprene are 2000 with the molar ratio of vanadium complex and co-catalyst:1:100.
The reaction temperature of the application is -10-50 DEG C, preferably 25 DEG C.
The reaction time of the application is 2-15h, preferably 5h.
The application, according to different polymeric reaction conditions, obtained polyisoprene number-average molecular weight is 1.1 × 104-
13.5×104, molecular weight distribution 1.8-3.5；The polyisoprene proportion of obtained cis- -1,4 structure of polyisoprene
Ranging from 63%-92%, the polyisoprene proportion ranging from 8%-37% of 3,4 structures.
Technique effect
Compared with prior art, vanadium complex preparation method of the present invention is simple, and the vanadium complex of preparation is used for isoprene
Polymerization compared with the catalyst system and catalyzing of document report, activity, selectivity, polyisoprene molecular weight all increase：Polymerization is anti-
Answer 5h that can realize that isoprene 100% converts；Cis- -1,4 polyisoprene contents may be up to 92%；Polyisoprene molecular weight
Up to 13.5 × 104；Molecular weight distribution is relatively narrow：1.8-3.5.
Specific implementation mode
Preparation example 1
The complexs of V [ONS] shown in formula II：
Under nitrogen atmosphere, sodium hydride (31.6mg, 1.3mmol) and 5mL tetrahydrofurans are added in dry reaction tube, it is cold
But to -30 DEG C, be added equimolar than ligand, shown in ligand structure formula such as formula (1), be warmed to room temperature reaction 4h, obtain ligand
Salting liquid.VCl is added in the reaction tube of another drying3(THF)3It is molten that (447mg, 1.2mmol) and 5mL tetrahydrofurans obtain vanadium
The salting liquid of ligand is added in vanadium solution, is stirred overnight at room temperature by liquid at room temperature.Concentration of reaction solution filters out sodium chloride
With the complete sodium hydride of unreacted, continuing to be concentrated into 5mL, 20mL n-hexanes is added, solid is precipitated, filtering vacuum is dried to constant weight,
Obtain the target product that dark brown solid is the present embodiment, yield 35%.
Mass spectral analysis：C18H20ClNO2SV[M-Cl]+Theoretical value：400.0343；Measured value：400.0351.
Elemental analysis：C18H20Cl2NO2SV：Theoretical value：C, 49.55%；H, 4.62%；N, 3.21%；Measured value：C,
49.61%；H, 4.53%；N, 3.23%.
Preparation example 2
V [ONS] complex shown in method formula III according to preparation example 1：Shown in ligand structure formula such as formula (2).
Filtering vacuum is dried to constant weight, and the target product that dark brown solid is the present embodiment, yield 39% are obtained.
Mass spectral analysis：C19H22ClNO2SV[M-Cl]+Theoretical value：414.0499；Measured value：414.0455.
Elemental analysis：Theoretical value：C19H22Cl2NO2SV：C, 50.68%；H, 4.92%；N, 3.11%；Measured value：C,
50.73%；H, 4.77%；N, 3.15%.
Preparation example 3
V [ONS] complex shown in method formula IV according to preparation example 1：Shown in ligand structure formula such as formula (3).
Filtering vacuum is dried to constant weight, and the target product that black solid is the present embodiment, yield 48% are obtained.
Mass spectral analysis：C23H22Cl2NO2SV[M-Cl]+Theoretical value：462.0499；Measured value：462.0473.
Elemental analysis：Theoretical value：C23H22Cl2NO2SV：C, 55.43%；H, 4.45%；N, 2.81%；Measured value：C,
53.97%；H, 4.51%；N, 2.75%.
Preparation example 4
V [ONS] complex shown in method formula V according to preparation example 1：Shown in ligand structure formula such as formula (4).
Filtering vacuum is dried to constant weight, and the target product that black solid is the present embodiment, yield 42% are obtained.
Mass spectral analysis：C26H36ClNO2SV[M-Cl]+Theoretical value：512.1595；Measured value：512.1611.
Elemental analysis：C26H36Cl2NO2SV：Theoretical value：C, 56.93%；H, 6.62%；N, 2.55%；Measured value：C,
56.87%；H, 6.69%；N, 2.51%.
Preparation example 5
V [ONS] complex shown in method formula VI according to preparation example 1：Shown in ligand structure formula such as formula (5).
Filtering vacuum is dried to constant weight, and the target product that dark green solid is the present embodiment, yield 31% are obtained.
Mass spectral analysis：C27H38ClNO2SV[M-Cl]+Theoretical value：526.1751；Measured value：526.1732.
Elemental analysis：C27H38Cl2NO2SV：Theoretical value：C, 57.65%；H, 6.81%；N, 2.49%；Measured value：C,
57.20%；H, 6.91%；N, 2.44%.
Preparation example 6
V [ONS] complex shown in method formula VII according to preparation example 1, shown in ligand structure formula such as formula (6).
Filtering vacuum is dried to constant weight, and the target product that dark green solid is the present embodiment, yield 41% are obtained.
Mass spectral analysis：C31H38Cl2NO2SV[M-Cl]+Theoretical value：574.1751；Measured value：574.1916.
Elemental analysis：Theoretical value：C31H38Cl2NO2SV：C, 60.98%；H, 6.27%；N, 2.29%；Measured value：C,
60.91%；H, 6.35%；N, 2.32%.
Embodiment 1
The embodiment is used for illustrating the polymerization using vanadium complex catalysis isoprene in the Formula II prepared：
25mL reaction tubes toast 3 times, under nitrogen atmosphere, sequentially add 4.4mg Formula II vanadium complex, 5mL toluene, 2mL
The hexane solution (a concentration of 1.5M of the methylaluminoxane in n-hexane) of isoprene and 3.33mL methylaluminoxane, 25
It after reacting 2h at DEG C, is quenched with the methanolic HCl solution of 0.2M, and be added in 100mL methanol, white solid filtering is precipitated, uses
A large amount of ethyl alcohol are washed rear vacuum and are drained.It is 75% to be computed yield, and cis--Isosorbide-5-Nitrae structure is 92%, and 3,4 structures are 8%, Mn=2.8
×104, Mw/Mn=2.1.
Embodiment 2
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, using formula III as major catalyst.
It is 35% to be computed yield, and cis--Isosorbide-5-Nitrae structure is 65%, and 3,4 structures are 35%, Mn=1.1 × 104, Mw/Mn=3.5.
Embodiment 3
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, using formula IV as major catalyst.
It is 69% to be computed yield, and cis--Isosorbide-5-Nitrae structure is 79%, and 3,4 structures are 21%, Mn=2.5 × 104, Mw/Mn=2.3.
Embodiment 4
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, using Formula V as major catalyst.Through
It is 73% to calculate yield, and cis--Isosorbide-5-Nitrae structure is 82%, and 3,4 structures are 18%, Mn=2.1 × 104, Mw/Mn=2.0.
Embodiment 5
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, using Formula IV as major catalyst.
It is 52% to be computed yield, and cis--Isosorbide-5-Nitrae structure is 77%, and 3,4 structures are 23%, Mn=2.7 × 104, Mw/Mn=2.0.
Embodiment 6
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, using Formula VII as major catalyst.
It is 66% to be computed yield, and cis--Isosorbide-5-Nitrae structure is 70%, and 3,4 structures are 30%, Mn=1.9 × 104, Mw/Mn=2.1.
Embodiment 7
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, extend the reaction time to 5h, through quenching
Yield is 100% after going out, and cis--Isosorbide-5-Nitrae structure is 91%, and 3,4 structures are 9%, Mn=2.9 × 104, Mw/Mn=2.0.
Embodiment 8
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, using triethyl aluminum as co-catalysis
15h is reacted in agent, does not have solid precipitation, yield 0% after being quenched.
Embodiment 9
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, it is urged using triisobutyl aluminium as helping
Agent reacts 15h, does not have solid precipitation, yield 0% after being quenched.
Embodiment 10
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, using aluminium diethyl monochloride as helping
Catalyst reaction 15h obtains yellow solid after being quenched, and yield 13%, nuclear-magnetism is characterized as cross-linking by-products.
Embodiment 11
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, using n-hexane as reaction dissolvent
5h is reacted, it is 48% to be computed yield, and cis--Isosorbide-5-Nitrae structure is 77%, and 3,4 structures are 23%, Mn=1.9 × 104, Mw/Mn=
1.8。
Embodiment 12
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, using pentane as reaction dissolvent
5h is reacted, it is 51% to be computed yield, and cis--Isosorbide-5-Nitrae structure is 69%, and 3,4 structures are 31%, Mn=3.0 × 104, Mw/Mn=
2.0。
Embodiment 13
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, using normal heptane as reaction dissolvent
5h is reacted, it is 45% to be computed yield, and cis--Isosorbide-5-Nitrae structure is 73%, and 3,4 structures are 27%, Mn=2.1 × 104, Mw/Mn=
1.9。
Embodiment 14
The polymerization of isoprene is carried out using 1 method of embodiment, unlike, it is molten using dichloromethane as reaction
5h is reacted in agent, and white solid is obtained after being quenched, and it is 39% to be computed yield, but all cross-linking by-products.
Embodiment 15
The polymerization of isoprene is carried out using 4 method of embodiment, unlike, use 0.67mL methylaluminoxane
(1.5M) obtains white solid after being quenched, it is 100% to be computed yield, and cis--Isosorbide-5-Nitrae structure is 91%, and 3,4 structures are 9%, Mn
=3.3 × 104, Mw/Mn=1.9.
Embodiment 16
The polymerization of isoprene is carried out using 4 method of embodiment, unlike, use 0.33mL methylaluminoxane
(1.5M) reacts 5h, and it is 58% to be computed yield, and cis--Isosorbide-5-Nitrae structure is 89%, and 3,4 structures are 11%, Mn=2.2 × 104,
Mw/Mn=2.0.
Embodiment 17
The polymerization of isoprene is carried out using 4 method of embodiment, unlike, use 0.067mL methylaluminoxane
(1.5M) reacts 15h, does not have solid precipitation, yield 0 after being quenched.
Embodiment 18
The polymerization of isoprene is carried out using 4 method of embodiment, unlike, reaction temperature is -10 DEG C, after being quenched
White solid is obtained, it is 25% to be computed yield, and cis--Isosorbide-5-Nitrae structure is 92%, and 3,4 structures are 8%, Mn=2.1 × 104, Mw/Mn
=1.8.
Embodiment 19
The polymerization of isoprene is carried out using 4 method of embodiment, unlike, reaction temperature is 50 DEG C, after being quenched
White solid is obtained, it is 11% to be computed yield, and cis--Isosorbide-5-Nitrae structure is 66%, and 3,4 structures are 34%, Mn=1.5 × 104, Mw/
Mn=2.3.
Embodiment 20
The polymerization of isoprene is carried out using 4 method of embodiment, unlike, reaction charging sequence changes：
Under nitrogen atmosphere, sequentially add that 5.5mg Formula II vanadium complex, 5mL toluene, (methylaluminoxane exists 0.67mL methylaluminoxane
A concentration of 1.5M in n-hexane) and 2mL isoprene liquid quenched after reacting 5h at 25 DEG C with the methanolic HCl solution of 0.2M
It goes out, and is added in 100mL methanol, white solid filtering is precipitated, washes rear vacuum with a large amount of ethyl alcohol and drains.Being computed yield is
95%, cis--Isosorbide-5-Nitrae structure is 92%, and 3,4 structures are 8%, Mn=2.8 × 104, Mw/Mn=2.0.
Claims (10)
1. a kind of vanadium complex, which is characterized in that the vanadium complex has structure shown in Formulas I：
Wherein, R1For in methyl, ethyl or phenyl one kind or two kinds or three kinds, R2For hydrogen-based or tertiary butyl；Its structural formula be with
One or two or more kinds in lower structure formula：
2. a kind of preparation method of vanadium complex described in claim 1, which is characterized in that (1) at room temperature, by tridentate ligand with
Sodium hydride reacts in tetrahydrofuran is prepared into sodium salt；(2) and then sodium salt reacts in tetrahydrofuran with the halide of vanadium, rear to locate
Vanudium complex is obtained after reason.
3. method according to claim 2, which is characterized in that step (1) described tridentate ligand is added to hydrogenation at -30 DEG C
The tetrahydrofuran solution of sodium is warmed to room temperature is reacted later, and the molar ratio of the tridentate ligand and sodium hydride is 1:1, reaction
Time is 4 hours；A concentration of 0.2-0.6mol/L of the sodium hydride in tetrahydrofuran；The tridentate ligand structural formula is following knot
One or two or more kinds in structure formula：
4. preparation method according to claim 2, it is characterised in that：The halide of step (2) sodium salt and vanadium rubs
You are than being 1:1, the reaction time is 4-8 hours；A concentration of 0.2-0.6mol/ of the halide of the vanadium in tetrahydrofuran
L。
5. a kind of application of vanudium complex described in claim 1 in isoprene polymerization, specially：In the reaction vessel according to
It is secondary that the vanudium complex, organic solvent, monomer isoprene, co-catalyst is added, or sequentially add the vanudium complex, have
Solvent, co-catalyst, monomer isoprene；Heating carries out polymerisation, and predominantly cis- -1 is obtained through post-processing after reaction,
The product of 4- polyisoprene.
6. application according to claim 5, which is characterized in that the molar ratio of monomer isoprene and vanadium complex is
(1000-5000):1；The volume ratio of organic solvent and monomer isoprene is (1-10):1.
7. application according to claim 5, which is characterized in that the temperature of polymerisation is -10-50 DEG C, and polymerization time is
2-15 hours.
8. application according to claim 6, which is characterized in that the organic solvent be toluene, paraxylene, n-hexane,
One or two or more kinds in hexamethylene, pentane, normal heptane, tetrahydrofuran or dichloromethane.
9. application according to claim 6, which is characterized in that the co-catalyst is trimethyl aluminium, triethyl aluminum, three different
One or two or more kinds in butyl aluminium, methylaluminoxane or the methylaluminoxane of modification；Methylaluminoxane (MAO) general structure
ForWherein n is the natural number of 4-40；Mole of the v element in aluminium element and vanadium complex in co-catalyst
Than for (100-1000):1.
10. according to any one of the claim 5-9 applications, which is characterized in that obtained polyisoprene number-average molecular weight
It is 1.1 × 104-13.5×104, molecular weight distribution 1.8-3.5；The polyisoprene proportion of cis- -1,4 structure is ranging from
63%-92%, the polyisoprene proportion ranging from 8%-37% of 3,4 structures.
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