CN111848669A - Vanadium complex catalyst containing phenoxy ligand and preparation method and application thereof - Google Patents
Vanadium complex catalyst containing phenoxy ligand and preparation method and application thereof Download PDFInfo
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- CN111848669A CN111848669A CN202010793415.4A CN202010793415A CN111848669A CN 111848669 A CN111848669 A CN 111848669A CN 202010793415 A CN202010793415 A CN 202010793415A CN 111848669 A CN111848669 A CN 111848669A
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- 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
- C08F136/20—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 unconjugated
Abstract
The invention discloses a vanadium complex catalyst containing a phenol-oxygen ligand, which has the following structural general formula:
wherein R is1、R2、R3、R4、R5、R′1、R′2、R′3、R′4、R′5Are one or more of hydrogen atom, methyl, isopropyl, phenyl and fluorine atom; the selectivity of a substituent group in the complex to double bonds in allene polymerization is researched, the knowledge blank in the field is made up, and the original innovation is strong; provides a new strategy for synthesizing the functionalized polydiene.
Description
Technical Field
The invention belongs to the field of polymer catalysis, and particularly relates to a vanadium complex catalyst containing a phenol-oxygen ligand, and a preparation method and application thereof.
Background
Allene derivatives are generally considered isomers of propargyl derivatives because they have cumulative double bonds and can be polymerized by a number of different methods, such as free radical, cationic, coordination, and zwitterionic polymerization. Since the nature of a polymer depends on its structure, the presence of any unique polymer structure necessarily affects the properties of the polymer. As such, allene and its derivatives can provide a number of functional materials through chemical modification (i.e., polymer reactions). Among them, polymers having an unsaturated system (e.g., polybutadiene) are representative synthetic precursors of functional materials because their chemical structures can be modified by many types of addition reactions. The polypropylenediene can be obtained by selective polymerization of any part of the cumulative double bonds of the allene derivative, and is expected to provide many unique characteristics since its unique structure can form a reactive propylene oxide or substituted propylene oxide directly attached to the backbone through a post-modification reaction. Such reactive polymers have been intensively studied because of their versatility as attractive synthetic precursors for functional materials due to the double bond addition reaction. In addition, the accumulated double bonds in the allene have high activity and multiple selectivity in the polymerization process, so that the selectivity of the polymer cannot be controlled, and the problems of wide molecular weight distribution, poor selectivity, low stereoregularity and the like of the polymer in the polymerization process are caused.
With the rapid development of analytical testing techniques, the chemical nature of allene has attracted attention from many chemists. Allene is useful as an intermediate for synthetic dyes, aerospace materials, pharmaceuticals, additives, and the like. Polymers and copolymers of allene are useful in the industries of elastomers, coatings, heat or corrosion resistant materials, and fibers. Owing to the high reactivity of the cumulative double bonds, allene compounds are widely used as a basis in the field of organic synthesis. They have also attracted the attention of polymer scientists because the corresponding polymers have double bonds, which can be converted into other functional materials by hydrogenation modification, epoxidation, hydrosilylation, and the like. However, the high reactivity of the cumulative double bonds makes it difficult to control the microstructure of the polymer by radical polymerization or cationic polymerization. The polymerization of allene can be well controlled by the use of coordination catalysts.
Therefore, the skilled person is working on the design and synthesis of a well-defined vanadium complex as an effective catalyst for the (co) polymerization of allene-based monomers, and remains an attractive project for organometallic and polymer research.
Disclosure of Invention
The invention aims to: the vanadium catalyst is used for polymerizing allene compounds and derivatives thereof, and the polymerization reaction process is controlled by regulating the steric hindrance and the electronic effect of the catalyst through a ligand structure to obtain a polymer with high selectivity and regular architecture.
In order to achieve the purpose, the invention provides the following technical scheme:
a vanadium complex catalyst containing a phenol-oxygen ligand has the following structural general formula:
wherein R is1、R2、R3、R4、R5、R′1、R′2、R′3、R′4、R′5Is one or more of hydrogen atom, methyl, isopropyl, phenyl and fluorine atom.
A preparation method of a vanadium complex catalyst containing a phenol-oxygen ligand comprises the following steps:
(1) weighing a reagent A in a Schlenk bottle in a nitrogen environment, slowly adding vanadium oxychloride, adding a solvent n-octane, placing the Schlenk bottle in an oil bath, stirring at the temperature of 130-135 ℃ for 20-24 hours, cooling at room temperature, filtering a crude product by diatomite, washing by dichloromethane to obtain a dark green solution, collecting filtrate, carrying out vacuum drying to obtain a brown solid, adding dichloromethane for dissolving, recrystallizing by n-hexane, standing at a low temperature for 1 day, removing the solution, carrying out vacuum drying on a residue to obtain a dark green solid product, and marking the dark green solid product as an intermediate a;
(2) weighing a reagent B and placing the reagent B into a reaction bottle in a nitrogen environment, adding a solvent n-hexane, refrigerating at low temperature for 1-2 hours, dropwise adding refrigerated n-butyllithium into the reaction bottle, quickly changing the system from a crystal state to a white turbid liquid, stirring at room temperature for 3-5 hours until the system is still in a white turbid state, standing, removing the solution, washing with n-hexane, and drying residues in vacuum to obtain white solid powder which is marked as an intermediate B;
(3) weighing an intermediate a, putting the intermediate a into a reaction bottle, adding a solvent alpha, refrigerating at low temperature for 1-2 hours, weighing an intermediate b, putting the intermediate b into the reaction bottle, changing the solution from blue to a reddish-brown solution, stirring at room temperature for 1-2 hours until the system is still the reddish-brown solution, drying in vacuum to obtain a brown oily substance, refrigerating at low temperature, washing with cold n-hexane, carrying out solid-liquid separation, and drying the residue in vacuum to obtain the vanadium complex catalyst containing the phenol-oxygen ligand;
wherein the reagent A is one of 2, 6-dimethylphenyl isocyanate, 2, 6-diisopropylphenyl isocyanate and 2, 4-difluorophenyl isocyanate;
the reagent B is one of m-dimethylphenol, m-diphenylphenol and pentafluorophenol;
the solvent alpha is one of toluene and n-hexane.
The application of the vanadium complex catalyst containing the phenol-oxygen ligand can be applied to catalyzing monomers with allene structures to polymerize, can realize the high-efficiency 2, 3-selective coordination polymerization of allene monomers, and the obtained polypropylene derivative has good stereoregularity and molecular weight distribution.
Preferably, the specific application process is as follows:
under the protection of anhydrous oxygen-free nitrogen, sequentially adding allene monomers and a solvent beta into a reaction bottle, then adding a vanadium complex catalyst containing a phenol-oxygen ligand and a cocatalyst, stirring for 12-36 hours at 25-80 ℃, adding methanol to terminate the reaction, then dropwise adding dilute hydrochloric acid to remove aluminum salt generated by the cocatalyst, washing the obtained product with methanol, and drying in vacuum until the quality is unchanged to obtain an allene derivative polymer;
wherein the allene monomer is one of phenyl allene, o-methoxy allene, p-methoxy allene and p-bromo allene, and the structural general formula is as follows:
in the formula, R ″)1、R″2、R″3、R″4、R″5Are one or more of hydrogen atom, methoxyl and bromine atom;
the solvent beta is one of toluene, dichloromethane and tetrahydrofuran;
the cocatalyst is one of triethyl aluminum and triisobutyl aluminum.
Preferably, when the allene monomer is phenyl allene, 1mmol of phenyl allene is added, the molar ratio of the vanadium complex catalyst containing the phenol-oxygen ligand to the phenyl allene to the cocatalyst is 1:200:50, and the amount of the solvent beta is 4-5 mL.
When in use, the general formula of coordination polymerization is as follows:
the vanadium complex catalyst containing the phenol-oxygen ligand, the preparation method and the application thereof have the following synthetic reaction general formula:
the vanadium complex catalyst containing the phenol-oxygen ligand provided by the invention has the following beneficial effects:
(1) the vanadium complex catalyst containing the phenol-oxygen ligand has the advantages of simple synthesis, no harsh requirements on experimental conditions, simple operation and easy reaction.
(2) The vanadium complex containing the phenoxy ligand is used for catalyzing the coordination polymerization reaction of allene for the first time, the steric hindrance and electronegativity of a substituent group are researched for the selectivity of accumulated double bonds, the knowledge blank in the field is made up, and the original innovation is very strong; provides a new strategy for synthesizing the functionalized polydiene.
Drawings
FIG. 1 shows ArNVCl, a product of example 2 of the present invention3(Ar＝2,4-F2Ph) was determined to be correct by distinguishing the signal peak.
Fig. 2,3 and 4 are a nuclear magnetic hydrogen spectrum, a carbon spectrum and a fluorine spectrum of the vanadium complex catalyst containing the phenoxy ligand synthesized in example 3 of the present invention, respectively, and the judgment that the substance is correct is made by the discrimination of signal peaks.
FIG. 5 is a nuclear magnetic hydrogen spectrum of the phenylpropadiene synthesized in example 4 of the present invention, and it was judged that the substance was correct by discriminating the signal peak.
FIGS. 6 and 7 are a nuclear magnetic hydrogen spectrum and a carbon spectrum of a polymer obtained by coordination polymerization of phenylpropadiene using a vanadium complex catalyst containing a phenol-oxygen ligand in example 5 of the present invention, respectively, and it can be judged that the obtained polymer is 1, 2-selective polyphenylpropyldiene by discrimination of nuclear magnetic hydrogen spectrum signal peaks; from the carbon spectrum, it can be seen that the polyphenylpropyldiene has good stereoregularity.
FIG. 8 is a GPC chart of the obtained polymer of phenylpropadiene catalyzed by vanadium complex catalyst containing phenoxy ligand in example 5 of the present invention, showing that the synthesized polymer can obtain good molecular weight, molecular weight distribution. The cocatalyst used in code 1 was triisobutylaluminum, 2 was triethylaluminum and 3 was trimethylaluminum, indicating that triisobutylaluminum is more stable to the active site.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of intermediate b- -lithium salt: under a nitrogen atmosphere, 100mL of n-hexane was added to M-diphenylphenol (1.97g,8mmol) to insolubilize and refrigerate at a low temperature for 1 hour, refrigerated n-butyllithium (3.76g,8.8mmol,1.1eq.,1.6M) was added dropwise thereto, the system rapidly changed from a crystalline state to a turbid white liquid, stirred at room temperature for 4 hours until the system remained turbid white, and the solution was allowed to stand, removed, washed with n-hexane (10 mL. times.2), and dried under vacuum to obtain 1.55g of a lithium salt as a white solid in a yield of 77%. The lithium salt has the following structural formula:
example 2
Preparation of intermediate a-vanadium trichloride: 2, 4-Difluorophenyl isocyanate (2.14g,13.7mmol) was charged to a Schlenk flask in a nitrogen atmosphere in VOCl3(3.56g,20.5mmol) was put into a Schlenk flask, 20mL of n-octane was added, and the reaction was carried out at 135 ℃ for 20 hours, with degassing at intervals during the reaction, and the reaction system was a dark blue solution after the reaction. Filtering with diatomaceous earth, washing with dichloromethane, collecting filtrate, vacuum drying to obtain brown solid, dissolving with a small amount of dichloromethane, recrystallizing with n-hexane, standing at-7 deg.C for 24 hr, removing solution, collecting solid, and vacuum drying to obtain ArNVCl3(Ar＝2,4-F2Ph) brown powder 2.30g, yield 59%. The structural formula of the vanadium trichloride is as follows:
example 3
Preparation of vanadium complex catalyst c containing a phenoxy ligand: taking ArNVCl in a nitrogen environment3(Ar＝2,4-F2Ph) (85mg,0.3mmol) was dissolved in 10mL of toluene, diphenylphenol (74mg,0.30mmol) was dissolved in 5mL of toluene, and the mixture was left to stand at-7 ℃ for 1 hour and added dropwise to ArNVCl3(Ar＝2,4-F2Ph) solution consisting of blueChanging the color into a reddish brown solution, stirring at room temperature for 1 hour to ensure that the system is still the reddish brown solution, drying in vacuum to obtain a brown oily substance, refrigerating at low temperature, washing for three times by using cold n-hexane, carrying out solid-liquid separation, and drying the solid to obtain 107mg of brown solid vanadium complex catalyst containing the phenol-oxygen ligand with the yield of 72 percent. The structural formula of the vanadium complex catalyst c containing the phenoxy ligand is as follows:
example 4
Preparation of monomer d-phenylpropadiene: paraformaldehyde (10.28g,343mmol,2.5eq.) and cuprous iodide (13.05g,69mmol,0.5eq.) were weighed and charged into a two-neck flask, a condenser tube, a tee and a nitrogen balloon were installed, nitrogen gas was replaced three times, diisopropylamine (24.96g,247mmol,1.8eq.) was injected into the system, 130mL of 1, 4-dioxane was further injected, phenylacetylene (14g,137mmol,1eq.) was further injected, and heating and refluxing were carried out at 110 ℃ for 14 hours. After the reaction is finished, deionized water is added into the system, ether extraction is carried out, an organic phase is collected, the organic phase is washed by water and a saturated sodium chloride solution, a water phase and a salt phase are extracted by ether, the organic phase is combined, diatomite is filtered to remove insoluble substances, the insoluble impurities in the system are separated by column chromatography for the first time (petroleum ether is used as an eluant), the product is purified by column chromatography for the second time (petroleum ether is used as the eluant), the filtrate is collected and dried in vacuum, and light yellow liquid 6.56g is obtained, and the yield is 41%. The structural formula of the monomer phenylpropadiene is as follows:
example 5
Coordination polymerization of phenylpropadiene: under the protection of anhydrous oxygen-free nitrogen, phenyl allene (116mg,1mmol) and 5mL of solvent toluene are sequentially added into a reaction bottle, and then vanadium complex catalyst V (NAr) containing phenol-oxygen ligand (OPhPh) is added2)Cl2(Ar＝2,4-F2Ph) (5 μmol), and triisobutylaluminum cocatalyst (0.25mmol), (phenoloxy ligand-containing vanadium complex catalyst: monomer: cocatalyst ═ 1:200:50) at room temperatureAfter stirring for 36 hours, methanol was added to terminate the reaction, dilute hydrochloric acid was added dropwise to remove aluminum salt produced in the cocatalyst, and the obtained product was washed with methanol and dried under vacuum until the mass was unchanged to obtain 22mg of polyphenylpropyldiene with a yield of 19%. The structural formula of the polyphenylpropyldiene is as follows:
the foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the present invention as defined in the accompanying claims.
Claims (6)
1. A vanadium complex catalyst containing a phenoxy ligand, characterized in that: the general structural formula is as follows:
wherein R is1、R2、R3、R4、R5、R′1、R′2、R′3、R′4、R′5Is one or more of hydrogen atom, methyl, isopropyl, phenyl and fluorine atom.
2. A method of preparing the vanadium complex catalyst containing a phenoxy ligand according to claim 1, comprising the steps of:
(1) weighing a reagent A in a Schlenk bottle in a nitrogen environment, slowly adding vanadium oxychloride, adding a solvent n-octane, placing the Schlenk bottle in an oil bath, stirring at the temperature of 130 ℃ and 135 ℃ for 20-24 hours, cooling at room temperature, filtering a crude product by diatomite, flushing dichloromethane to obtain a dark green solution, collecting filtrate, carrying out vacuum drying to obtain a brown solid, adding dichloromethane for dissolving, recrystallizing n-hexane, standing at a low temperature for 20-25 hours, removing the solution, carrying out vacuum drying on a residue, and obtaining a dark green solid product which is marked as an intermediate a;
(2) weighing a reagent B and placing the reagent B into a reaction bottle in a nitrogen environment, adding a solvent n-hexane, refrigerating at low temperature for 1-2 hours, dropwise adding refrigerated n-butyllithium into the reaction bottle, quickly changing the system from a crystal state to a white turbid liquid, stirring at room temperature for 3-5 hours until the system is still in a white turbid state, standing, removing the solution, washing with n-hexane, and drying residues in vacuum to obtain white solid powder which is marked as an intermediate B;
(3) weighing an intermediate a, putting the intermediate a into a reaction bottle, adding a solvent alpha, refrigerating at low temperature for 1-2 hours, weighing an intermediate b, putting the intermediate b into the reaction bottle, changing the solution from blue to a reddish-brown solution, stirring at room temperature for 1-2 hours until the system is still the reddish-brown solution, drying in vacuum to obtain a brown oily substance, refrigerating at low temperature, washing with cold n-hexane, carrying out solid-liquid separation, and drying the residue in vacuum to obtain the vanadium complex catalyst containing the phenol-oxygen ligand;
wherein the reagent A is one of 2, 6-dimethylphenyl isocyanate, 2, 6-diisopropylphenyl isocyanate and 2, 4-difluorophenyl isocyanate;
the reagent B is one of m-dimethylphenol, m-diphenylphenol and pentafluorophenol;
the solvent alpha is one of toluene and n-hexane.
3. Use of a vanadium complex catalyst containing a phenoxy ligand according to claim 1, wherein: can be applied to catalyzing the polymerization of the monomer with the allene structure.
4. Use of the vanadium complex catalyst containing a phenolic oxo ligand according to claim 3, wherein: can realize the efficient 2, 3-selective coordination polymerization of allene monomers, and the obtained polypropylene derivative has good stereoregularity and molecular weight distribution.
5. The application of the vanadium complex catalyst containing the phenoxy ligand according to claim 3, which comprises the following steps:
under the protection of anhydrous oxygen-free nitrogen, sequentially adding allene monomers and a solvent beta into a reaction bottle, then adding a vanadium complex catalyst containing a phenol-oxygen ligand and a cocatalyst, stirring for 12-36 hours at 25-80 ℃, adding methanol to terminate the reaction, then dropwise adding dilute hydrochloric acid to remove aluminum salt generated by the cocatalyst, washing the obtained product with methanol, and drying in vacuum until the quality is unchanged to obtain an allene derivative polymer;
wherein the allene monomer is one of phenyl allene, o-methoxy allene, p-methoxy allene and p-bromo allene, and the structural general formula is as follows:
in the formula, R ″)1、R″2、R″3、R″4、R″5Are one or more of hydrogen atom, methoxyl and bromine atom;
the solvent beta is one of toluene, dichloromethane and tetrahydrofuran;
the cocatalyst is one of triethyl aluminum and triisobutyl aluminum.
6. Use of the vanadium complex catalyst containing a phenolic oxo ligand according to claim 5, wherein:
when the added allene monomer is phenyl allene, 1mmol of phenyl allene is added, the molar ratio of the vanadium complex catalyst containing the phenol-oxygen ligand to the phenyl allene to the cocatalyst is 1:200:50, and the amount of the solvent beta is 4-5 mL.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114195918A (en) * | 2021-12-31 | 2022-03-18 | 常州汉韦聚合物有限公司 | Transition metal complex catalyst containing double anion ligands and application thereof in olefin polymerization |
| CN114702520A (en) * | 2022-04-15 | 2022-07-05 | 合肥工业大学 | Vanadium complex catalyst containing large steric hindrance phenol oxygen ligand and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002249510A (en) * | 2001-02-26 | 2002-09-06 | Asahi Kasei Corp | Polymerization catalyst of olefin polymer and method for manufacturing olefin polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002249510A (en) * | 2001-02-26 | 2002-09-06 | Asahi Kasei Corp | Polymerization catalyst of olefin polymer and method for manufacturing olefin polymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195918A (en) * | 2021-12-31 | 2022-03-18 | 常州汉韦聚合物有限公司 | Transition metal complex catalyst containing double anion ligands and application thereof in olefin polymerization |
| CN114702520A (en) * | 2022-04-15 | 2022-07-05 | 合肥工业大学 | Vanadium complex catalyst containing large steric hindrance phenol oxygen ligand and preparation method and application thereof |
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