CN108659036B - Vanadium complex, preparation method thereof and application thereof in isoprene polymerization - Google Patents
Vanadium complex, preparation method thereof and application thereof in isoprene polymerization Download PDFInfo
- Publication number
- CN108659036B CN108659036B CN201810402184.2A CN201810402184A CN108659036B CN 108659036 B CN108659036 B CN 108659036B CN 201810402184 A CN201810402184 A CN 201810402184A CN 108659036 B CN108659036 B CN 108659036B
- Authority
- CN
- China
- Prior art keywords
- isoprene
- vanadium
- vanadium complex
- complex
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 47
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 4
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 28
- 239000003054 catalyst Substances 0.000 abstract description 16
- 239000003446 ligand Substances 0.000 abstract description 16
- 229920003049 isoprene rubber Polymers 0.000 abstract description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 12
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000104 sodium hydride Inorganic materials 0.000 abstract description 8
- 239000012312 sodium hydride Substances 0.000 abstract description 8
- 159000000000 sodium salts Chemical class 0.000 abstract description 8
- 229920001971 elastomer Polymers 0.000 abstract description 5
- 239000005060 rubber Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 150000004820 halides Chemical class 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 150000001638 boron Chemical class 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 230000020335 dealkylation Effects 0.000 abstract 1
- 238000006900 dealkylation reaction Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 27
- 239000007787 solid Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000010791 quenching Methods 0.000 description 9
- 230000000171 quenching effect Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 238000004949 mass spectrometry Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000208688 Eucommia Species 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 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
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- AZLYZRGJCVQKKK-UHFFFAOYSA-N dioxohydrazine Chemical compound O=NN=O AZLYZRGJCVQKKK-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- -1 vanadium halide Chemical class 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 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 invention provides a vanadium complex, a preparation method thereof and application thereof in isoprene polymerization, relates to the technical field of high polymer material preparation, and particularly belongs to the field of polyisoprene rubber synthesis. In order to solve the problems of low selectivity of a complex catalyzed isoprene polymerization polymer structure, low activity of a vanadium catalyst and the like, the vanadium complex provided by the invention is prepared into sodium salt by reacting a tridentate ligand with sodium hydride in tetrahydrofuran at room temperature; then the sodium salt reacts with the halide of vanadium in tetrahydrofuran, and the sodium salt is obtained after post-treatment. Isoprene reacts in an organic solvent under the action of the vanadium complex and a cocatalyst to prepare the isoprene rubber mainly comprising cis-1 and 4. The vanadium complex of the invention has simple preparation method, is insensitive to temperature, is cheaper and easily obtained compared with the polymerization reaction using a boron salt dealkylation reagent, effectively enlarges the application of vanadium metal in olefin polymerization reaction, and has good industrial value.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, and particularly belongs to the field of synthesis of polyisoprene rubber.
Background
Isoprene rubber is a rubber obtained by polymerizing isoprene monomers under the action of a catalyst, is also called synthetic natural rubber, is widely applied to people's lives, such as tires, medical materials, golf ball shells and the like, and has attracted attention in academic research and industrial production. Structurally, polyisoprenes can be divided into 1, 2-isoprene rubber, 3, 4-isoprene rubber, trans-1, 4-isoprene rubber and cis-1, 4-isoprene rubber. Isoprene rubbers of different structures exhibit properties that vary greatly. For example, cis-1, 4-isoprene rubber is closer to natural rubber in structure and performance, and is widely applied to the rubber processing fields of tires, rubber tubes and the like; the trans-1, 4-isoprene rubber has the performance more similar to that of eucommia rubber, and has excellent dynamic mechanical property and good performanceGood wear resistance; the 3, 4-isoprene rubber has good wet gripping performance and high-temperature low hysteresis loss, and is a synthetic rubber material with low heat generation and high wet skid resistance. At present, a great deal of research reports that isoprene is catalyzed and polymerized, and isoprene rubber with different structures is obtained by regulating and controlling the reaction conditions of a catalyst and a cocatalyst. The catalyst plays a crucial role in isoprene polymerization and is the core content in isoprene rubber preparation research. The research on isoprene polymerization catalyzed by transition metal mainly focuses on the III and IV families, wherein the isoprene rubber is synthesized by mainly utilizing titanium catalysts and rare earth catalysts in industry, and the cis-1, 4-structure can reach 98%. In addition, late transition metal catalysts have also been extensively studied in isoprene polymerization, such as iron and cobalt complexes. However, there are few studies on the use of intermediate transition metals in the preparation of isoprene rubber. Among them, the vanadium-based catalyst was applied to olefin polymerization as early as 1950, and is one of the earliest homogeneous polymerization systems. In vanadium-catalyzed heterogeneous systems, VCl3、VCl4、VOCl3、V(acac)3And VCl33THF can catalyze isoprene to polymerize under the combined action of an alkylaluminum cocatalyst to obtain the trans-1, 4-structure isoprene rubber. However, in these systems, the vanadium-based catalyst is easily reduced to a low-valent substance, which deactivates the catalyst, and the catalytic efficiency of the above systems is low. There are two main methods for solving the problem of catalyst deactivation, one is to add an oxidant into the catalyst system, and the other is to introduce a ligand on the vanadium metal to further stabilize the central metal. The Zinck group reported V [ ONNO ]]The complex catalyzes isoprene polymerization, the catalytic activity is high, but the molecular weight of polyisoprene is low, the selectivity of the polymerization reaction is not high, and the ratio of the 3,4 structure to the cis-1, 4 structure in the polyisoprene is 68/32. Therefore, the search for vanadium-based catalysts with high activity and high stereoselectivity to realize the controllable polymerization of isoprene is a challenge in academia.
Disclosure of Invention
The invention aims to provide a novel vanadium complex and a preparation method thereof on the basis of the prior art, and simultaneously relates to application of the catalyst in isoprene polymerization reaction to obtain polyisoprene with high cis-1, 4, high molecular weight and narrow molecular weight distribution.
In order to achieve the purpose, the invention provides a vanadium complex, and the structural formula of the vanadium complex is shown as a formula I.
The preparation method of the vanadium complex comprises the steps of adding a ligand into a tetrahydrofuran solution of sodium hydride at the temperature of-30 ℃, heating to room temperature for reacting for 4 hours, and transferring the clear solution to VCl with an equal molar ratio at room temperature3(THF)3Reacting in tetrahydrofuran solution, and post-treating and drying to constant weight.
The invention is realized by the following technical scheme:
the invention provides a vanadium complex. The vanadium complex has a structure shown in formula I:
wherein R is1Is one or two or three of methyl, ethyl or phenyl, R2Is hydrogen radical or tertiary butyl; the structural formula is one or more than two of the following structural formulas:
the invention also provides a preparation method of the vanadium complex, which comprises the following steps: (1) reacting a tridentate ligand with sodium hydride in tetrahydrofuran at room temperature to prepare sodium salt; (2) then the sodium salt reacts with the halide of vanadium in tetrahydrofuran, and the vanadium complex is obtained after post-treatment.
The preparation method of the vanadium complex comprises the steps of (1) adding the tridentate ligand into a tetrahydrofuran solution of sodium hydride at the temperature of-30 ℃, then heating to room temperature for reaction, wherein the molar ratio of the tridentate ligand to the sodium hydride is 1:1, and the reaction time is 4 hours; the concentration of sodium hydride in tetrahydrofuran is 0.2-0.6 mol/L; the structural formula of the tridentate ligand is one or two of the following structural formulasThe method comprises the following steps:
in the preparation method of the vanadium complex, the molar ratio of the sodium salt to the halide of the vanadium in the step (2) is 1:1, and the reaction time is 4-8 hours; the concentration of the vanadium halide in tetrahydrofuran is 0.2-0.6 mol/L.
The invention also provides application of the vanadium complex in catalyzing isoprene polymerization, and the application comprises the step of reacting under the action of an organic solvent, the catalyst and a cocatalyst to prepare cis-1, 4-based polyisoprene. The method specifically comprises the following steps: sequentially adding the vanadium complex, the organic solvent, the monomer isoprene and the cocatalyst into a reaction vessel, or sequentially adding the vanadium complex, the organic solvent, the cocatalyst and the monomer isoprene; heating to carry out polymerization reaction, and carrying out post-treatment after the reaction to obtain a product mainly comprising cis-1, 4-polyisoprene.
The application and the preferable feeding sequence are as follows: after the vanadium complex and the organic solvent are respectively added, isoprene and a cocatalyst are sequentially added. The molar ratio of the monomer isoprene to the vanadium complex is (1000-; the volume ratio of the organic solvent to the monomer isoprene is (1-10): 1. The organic solvent is one or more of toluene, p-xylene, n-hexane, cyclohexane, n-pentane, n-heptane, tetrahydrofuran and dichloromethane, preferably toluene. The cocatalyst is one or more than two of trimethylaluminum, triethylaluminum, triisobutylaluminum, methylaluminoxane or modified methylaluminoxane; the general structural formula of the Methylaluminoxane (MAO) is
Wherein n is a natural number of 4 to 40; the molar ratio of the aluminum element in the cocatalyst to the vanadium element in the vanadium complex is (100- & ltSUB- & gt 1000) & gt 1.
Preferably, the molar ratio of isoprene to vanadium complex and cocatalyst is 2000:1: 100.
The reaction temperature for the application is-10 to 50 deg.C, preferably 25 deg.C.
The reaction time for the application is 2-15h, preferably 5 h.
According to different polymerization reaction conditions, the number average molecular weight of the obtained polyisoprene is 1.1 x 104-13.5×104The molecular weight distribution is 1.8-3.5; the proportion range of the polyisoprene with the obtained polyisoprene cis-1, 4 structure is 63% -92%, and the proportion range of the polyisoprene with the 3,4 structure is 8% -37%.
Technical effects
Compared with the prior art, the preparation method of the vanadium complex is simple, and compared with a catalytic system reported in the literature, the activity, the selectivity and the polyisoprene molecular weight of the prepared vanadium complex used for isoprene polymerization are improved: the 100 percent conversion of isoprene can be realized after 5 hours of polymerization reaction; the cis-1, 4 polyisoprene content can be as high as 92%; the molecular weight of the polyisoprene can be as high as 13.5 multiplied by 104(ii) a The molecular weight distribution is narrow: 1.8-3.5.
Detailed Description
Preparation example 1
Preparing a V [ ONS ] complex of formula II:
under the nitrogen atmosphere, adding sodium hydride (31.6mg,1.3mmol) and 5mL tetrahydrofuran into a dry reaction tube, cooling to-30 ℃, adding an equimolar ratio ligand, wherein the structural formula of the ligand is shown as a formula (1), and heating to room temperature for reacting for 4 hours to obtain a salt solution of the ligand. VCl was added to the other dry reaction tube3(THF)3(447mg,1.2mmol) and 5mL of tetrahydrofuran to give a vanadium solution, and the salt solution of the ligand was added to the vanadium solution at room temperature and stirred at room temperature overnight. Concentrating the reaction solution, filtering out sodium chloride and sodium hydride which is not completely reacted, continuously concentrating to 5mL, adding 20mL of n-hexane to precipitate a solid, filtering, and drying in vacuum to constant weight to obtain a dark brown solid which is the target product in the embodiment, wherein the yield is 35%.
Mass spectrometry analysis: c18H20ClNO2SV[M-Cl]+Theoretical value: 400.0343, respectively; measured value: 400.0351.
elemental analysis: c18H20Cl2NO2SV: theoretical value: c, 49.55%; h,4.62Percent; n, 3.21%; measured value: c, 49.61%; h, 4.53%; and N, 3.23%.
Preparation example 2
The V [ ONS ] complex of formula III was prepared according to the procedure of preparation 1: the structural formula of the ligand is shown as a formula (2).
The mixture is filtered and dried in vacuum to constant weight, and a dark brown solid which is the target product of the embodiment is obtained, and the yield is 39%.
Mass spectrometry analysis: c19H22ClNO2SV[M-Cl]+Theoretical value: 414.0499, respectively; 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%; and N,3.15 percent.
Preparation example 3
The preparation of the V [ ONS ] complex of formula IV was carried out according to the procedure of preparation 1: the structural formula of the ligand is shown as a formula (3).
And filtering, vacuum drying to constant weight to obtain black solid which is the target product of the embodiment, and the yield is 48%.
Mass spectrometry analysis: c23H22Cl2NO2SV[M-Cl]+Theoretical value: 462.0499, respectively; 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%; and N,2.75 percent.
Preparation example 4
The preparation of the V [ ONS ] complex of formula V was carried out according to the procedure of preparation 1: the structural formula of the ligand is shown as a formula (4).
And filtering, vacuum drying to constant weight to obtain black solid which is the target product of the embodiment, and the yield is 42%.
Mass spectrometry analysis: c26H36ClNO2SV[M-Cl]+Theoretical value: 512.1595, respectively; 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 percent.
Preparation example 5
The V [ ONS ] complex of formula VI is prepared according to the procedure of preparation 1: the structural formula of the ligand is shown as a formula (5).
And filtering, vacuum drying to constant weight to obtain dark green solid which is the target product of the embodiment, wherein the yield is 31%.
Mass spectrometry analysis: c27H38ClNO2SV[M-Cl]+Theoretical value: 526.1751, respectively; 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 percent.
Preparation example 6
The VONS complex shown in formula VII is prepared according to the method of preparation example 1, and the ligand structural formula is shown in formula (6).
And filtering, vacuum drying to constant weight to obtain dark green solid which is the target product of the embodiment, wherein the yield is 41%.
Mass spectrometry analysis: c31H38Cl2NO2SV[M-Cl]+Theoretical value: 574.1751, respectively; 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 percent.
Example 1
This example serves to illustrate the use of the prepared vanadium complex of formula II to catalyze the polymerization of isoprene:
baking the 25mL reaction tube for 3 times, adding 4.4mg vanadium complex of formula II, 5mL toluene, 2mL isoprene and 3.33mL methylaluminoxane solution in n-hexane (the concentration of methylaluminoxane in n-hexane is 1.5M) in sequence under nitrogen atmosphere, reacting for 2h at 25 ℃, quenching with 0.2M methanol hydrochloric acid solution, adding into 100mL methanol, precipitating white solid, filtering, washing with a large amount of ethanol, and vacuum-pumping to dry. The calculated yield was 75%, cis92% for-1, 4 structure, 8% for 3,4 structure, Mn＝2.8×104，Mw/Mn＝2.1。
Example 2
Isoprene polymerization was carried out by the method of example 1, except that formula III was used as the procatalyst. The calculated yield was 35%, cis-1, 4 structure 65%, 3,4 structure 35%, Mn＝1.1×104，Mw/Mn＝3.5。
Example 3
Isoprene polymerization was carried out by the method of example 1, except that formula IV was used as the procatalyst. The calculated yield was 69%, the cis-1, 4 structure was 79%, the 3,4 structure was 21%, Mn＝2.5×104，Mw/Mn＝2.3。
Example 4
Isoprene polymerization was carried out by the method of example 1, except that formula V was used as the main catalyst. The calculated yield was 73%, cis-1, 4 structure 82%, 3,4 structure 18%, Mn＝2.1×104，Mw/Mn＝2.0。
Example 5
Isoprene polymerization was carried out using the method of example 1, except that formula VI was used as the procatalyst. The calculated yield was 52%, the cis-1, 4 structure was 77%, the 3,4 structure was 23%, Mn＝2.7×104，Mw/Mn＝2.0。
Example 6
Isoprene polymerization was carried out by the method of example 1, except that formula VII was used as the procatalyst. The calculated yield was 66%, the cis-1, 4 structure was 70%, the 3,4 structure was 30%, Mn＝1.9×104，Mw/Mn＝2.1。
Example 7
Isoprene polymerization was carried out by the method of example 1, except that the reaction time was prolonged to 5 hours, the yield after quenching was 100%, the cis-1, 4 structure was 91%, the 3,4 structure was 9%, and M wasn＝2.9×104，Mw/Mn＝2.0。
Example 8
Isoprene was polymerized by the method of example 1, except that triethylaluminum was used as a co-catalyst and reacted for 15 hours, and no solid was precipitated after quenching, and the yield was 0%.
Example 9
Isoprene was polymerized by the method of example 1, except that triisobutylaluminum was used as a co-catalyst and reacted for 15 hours, and no solid was precipitated after quenching, and the yield was 0%.
Example 10
Isoprene was polymerized by the method of example 1, except that diethylaluminum chloride was used as a cocatalyst and reacted for 15h, and quenched to give a yellow solid with a yield of 13% and nuclear magnetic characterization as a crosslinking byproduct.
Example 11
Isoprene polymerization was carried out by the method of example 1, except that n-hexane was used as a reaction solvent for 5 hours, and the calculated yield was 48%, the cis-1, 4 structure was 77%, the 3,4 structure was 23%, and M wasn＝1.9×104，Mw/Mn＝1.8。
Example 12
Isoprene polymerization was carried out by the method of example 1, except that n-pentane was used as the reaction solvent for 5 hours, and the calculated yield was 51%, the cis-1, 4 structure was 69%, the 3,4 structure was 31%, and M wasn＝3.0×104，Mw/Mn＝2.0。
Example 13
Isoprene was polymerized by the method of example 1, except that n-heptane was used as the reaction solvent for 5 hours, and the calculated yield was 45%, the cis-1, 4 structure was 73%, the 3,4 structure was 27%, and M wasn＝2.1×104，Mw/Mn＝1.9。
Example 14
Isoprene was polymerized by the method of example 1, except that dichloromethane was used as the reaction solvent and reacted for 5 hours, and after quenching, a white solid was obtained with a calculated yield of 39%, but all were crosslinking by-products.
Example 15
Isoprene polymerization was carried out by the method of example 4, except that 0.67mL of methylaluminoxane (1.5M) was used and quenching was carried out to obtain a white solid with a calculated yield of 100%, a cis-1, 4 structure of 91%, a 3,4 structure of 9%, and a Mn＝3.3×104，Mw/Mn＝1.9。
Example 16
Isoprene polymerization was carried out by the method of example 4, except that 0.33mL of methylaluminoxane (1.5M) was used for 5h, the calculated yield was 58%, the cis-1, 4 structure was 89%, the 3,4 structure was 11%, and M wasn＝2.2×104，Mw/Mn＝2.0。
Example 17
Isoprene was polymerized by the method of example 4, except that 0.067mL of methylaluminoxane (1.5M) was used for the reaction for 15 hours, no solid was precipitated after quenching, and the yield was 0.
Example 18
Isoprene was polymerized by the method of example 4, except that the reaction temperature was-10 deg.C, and a white solid was obtained after quenching, the calculated yield was 25%, the cis-1, 4 structure was 92%, the 3,4 structure was 8%, and M wasn＝2.1×104，Mw/Mn＝1.8。
Example 19
Isoprene was polymerized by the method of example 4, except that the reaction temperature was 50 ℃, and a white solid was obtained after quenching, the calculated yield was 11%, the cis-1, 4 structure was 66%, the 3,4 structure was 34%, and M wasn＝1.5×104，Mw/Mn＝2.3。
Example 20
Isoprene was polymerized by the method of example 4, except that the order of the reaction feeds was changed: under nitrogen atmosphere, sequentially adding 5.5mg of vanadium compound of formula IIThe mixture, 5mL of toluene, 0.67mL of methylaluminoxane (methylaluminoxane concentration in n-hexane: 1.5M), and 2mL of isoprene solution were reacted at 25 ℃ for 5 hours, quenched with 0.2M of methanol hydrochloric acid solution, added to 100mL of methanol, precipitated as a white solid, filtered, washed with a large amount of ethanol, and vacuum-dried. The calculated yield was 95%, the cis-1, 4 structure was 92%, the 3,4 structure was 8%, Mn＝2.8×104，Mw/Mn＝2.0。
Claims (3)
1. The application of a vanadium complex in isoprene polymerization is characterized in that: sequentially adding the vanadium complex, the organic solvent, the monomer isoprene and the cocatalyst into a reaction vessel, or sequentially adding the vanadium complex, the organic solvent, the cocatalyst and the monomer isoprene; carrying out polymerization reaction, and carrying out post-treatment after the reaction to obtain a product mainly comprising cis-1, 4-polyisoprene;
the structural formula of the vanadium complex is one of the following structural formulas:
the organic solvent is n-hexane; the polymerization time is 2 to 15 hours;
when the structural formula of the vanadium complex is V, the reaction temperature is-10 ℃ or 25 ℃;
when the structural formula of the vanadium complex is II, III, IV, VI or VII, the reaction temperature is 25 ℃.
2. The use according to claim 1, wherein the molar ratio of monomeric isoprene to vanadium complex is (1000- & 5000): 1; the volume ratio of the organic solvent to the monomer isoprene is (1-10): 1.
3. Use according to any one of claims 1 to 2, wherein the polyisoprene obtained has a number-average molecular weight of 1.1 x 104-13.5×104The molecular weight distribution is 1.8-3.5; poly of cis-1, 4 structureThe proportion range of isoprene is 63% -92%, and the proportion range of 3,4 structural polyisoprene is 8% -37%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810402184.2A CN108659036B (en) | 2018-04-28 | 2018-04-28 | Vanadium complex, preparation method thereof and application thereof in isoprene polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810402184.2A CN108659036B (en) | 2018-04-28 | 2018-04-28 | Vanadium complex, preparation method thereof and application thereof in isoprene polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108659036A CN108659036A (en) | 2018-10-16 |
| CN108659036B true CN108659036B (en) | 2021-01-01 |
Family
ID=63781471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810402184.2A Active CN108659036B (en) | 2018-04-28 | 2018-04-28 | Vanadium complex, preparation method thereof and application thereof in isoprene polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108659036B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805429A (en) * | 2022-04-21 | 2022-07-29 | 中国科学院青岛生物能源与过程研究所 | Pyridine imine vanadium complex, preparation method thereof and application thereof in conjugated olefin polymerization |
| US20240209188A1 (en) * | 2022-12-14 | 2024-06-27 | The Goodyear Tire & Rubber Company | Synthetic polyisoprene and method of synthesizing polyisoprene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402694A (en) * | 2008-11-17 | 2009-04-08 | 中国科学院长春应用化学研究所 | Three-tooth salicylaldehyde imine vanadium olefin polymerizing catalyst, preparation and uses thereof |
-
2018
- 2018-04-28 CN CN201810402184.2A patent/CN108659036B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402694A (en) * | 2008-11-17 | 2009-04-08 | 中国科学院长春应用化学研究所 | Three-tooth salicylaldehyde imine vanadium olefin polymerizing catalyst, preparation and uses thereof |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis,Structural Characterization,and Olefin Polymerization Behavior of Vanadium(III) Complexes Bearing Tridentate Schiff Base Ligands;Ji-Qian Wu等;《Organometallics》;20090218;第28卷;方案2-3、第1818页右栏、表1-2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108659036A (en) | 2018-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110452272B (en) | Bipyridine iron complex, preparation method thereof and application thereof in conjugated diene polymerization | |
| CN108586641B (en) | High-efficiency iron-based catalyst for catalyzing isoprene polymerization and preparation method and application thereof | |
| CN112442092B (en) | 6-methoxypyridine iron imine complex, preparation method thereof and application thereof in preparation of high-cis-poly conjugated diene | |
| EP3808753B1 (en) | Bipyridine iron complex, preparation method thereof and application in polymerization of conjugated diene | |
| CN109912732B (en) | Bond-forming pyridylamine iron-based catalyst and preparation method and application thereof | |
| CN108659036B (en) | Vanadium complex, preparation method thereof and application thereof in isoprene polymerization | |
| CN112062787B (en) | Pyridine imine titanium complex and application thereof in conjugated diene catalytic polymerization | |
| CN111116806A (en) | Preparation method of olefin-unsaturated carboxylic acid copolymer | |
| CN110283264A (en) | A kind of bipyridyl iron complex and the preparation method and application thereof | |
| WO2023050789A1 (en) | Iron-based conjugated diene polymer and preparation method therefor | |
| CN111303214B (en) | Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same | |
| CN108659055B (en) | Iron complex based on flexible framework, preparation method thereof and application thereof in isoprene polymerization | |
| CN108641026B (en) | Application of benzyl imine pyridine iron complex in preparation of isoprene rubber | |
| CN106188356A (en) | A kind of Tetraheteropoly rare earth catalyst system and catalyzing and its preparation method and application | |
| CN112707937B (en) | Heteroaromatic ring tridentate pyridine imine iron complex, preparation method thereof and application thereof in catalysis of polymerization of conjugated diene | |
| CN115850546A (en) | Method for preparing low-1,4 structure poly-conjugated diene by adopting iron-based phosphine-containing catalytic system | |
| CN111303325B (en) | Efficient controllable preparation method of polyisoprene | |
| CN114805685A (en) | Polar conjugated olefin polymer and preparation method and application thereof | |
| CN114736245B (en) | Pyridine-2-oxime-iron complex, preparation method thereof and application thereof in preparation of conjugated diene rubber | |
| WO2022183467A1 (en) | Heteroaromatic ring tridentate pyridine imine iron complex, preparation method therefor, and application thereof in catalysis of conjugated diene polymerization | |
| CN108864343B (en) | Binuclear (alpha-diimine) nickel/palladium olefin catalyst, preparation and application | |
| CN111848840A (en) | Silica gel supported zirconium-vanadium bimetallic complex, and preparation method and application thereof | |
| CN114805429A (en) | Pyridine imine vanadium complex, preparation method thereof and application thereof in conjugated olefin polymerization | |
| CN115873045B (en) | N, N-bidentate iron carboxylate complex, preparation method and application thereof in conjugated diene polymerization | |
| CN112175122B (en) | Application of tridentate salicylaldiminato titanium complex, poly-conjugated diene, and preparation method and application of poly-conjugated diene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |