CN111995734A - Cage-type polysilsesquioxane-based star-shaped hybrid spiral polyisonitrile and preparation method and application thereof - Google Patents
Cage-type polysilsesquioxane-based star-shaped hybrid spiral polyisonitrile and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a cage-type Polysilsesquioxane (POSS) -based star-shaped hybrid spiral polyisonitrile as well as a preparation method and application thereof, and the structure is shown as the following general formula:
in the formula (I), the compound is shown in the specification,
during preparation, aminated POSS is synthesized, alkynyl is introduced through amidation reaction, organic/inorganic hybrid palladium catalyst is obtained through reaction with palladium, and isonitrile polymerization is initiated to prepare the catalystPreparing POSS-based star-shaped hybrid spiral polyisonitrile. According to the invention, organic materials and inorganic materials are combined, and the prepared catalyst has good catalytic capability, and the star-shaped hybrid spiral polyisonitrile is easy and convenient to obtain. The polymer obtained by the catalyst is of an eight-arm star-shaped spiral structure, and has high molecular weight and narrow molecular weight distribution. Has great potential application value in the fields of self-assembly, medicine loading, chiral separation, dye adsorption and the like.
Description
Technical Field
The invention belongs to the field of polymer catalytic reaction and preparation of functional polymers, and particularly relates to a cage-type Polysilsesquioxane (POSS) -based star-shaped hybrid spiral polyisocyanamide and a preparation method and application thereof.
Background
The polyisonitrile is an artificially synthesized polymer with stable helical conformation, which can be used in various aspects such as chiral recognition, enantiomer separation, asymmetric catalysis and the like. The monomer is easy to obtain and the polymerization method is simple, so that the method is popular. In the past decades, various functional types of polyisonitriles have been reported in succession, however, these polyisonitriles are mostly linear, and studies on hybrid star polyisonitriles have been rare. Compared with linear polymers, the star polymer has smaller dynamic mechanical size in solution and has the characteristic of low solution and bulk viscosity, which is of great significance to the processing of the polymer.
Cage-like silsesquioxane (POSS) is a novel material with an inorganic framework formed by linking Si-O-Si as an inner core and substituent groups on the periphery. It has cage core and organic branch chain of inorganic silicon-oxygen-silicon structure, and is one excellent molecular level nanometer organic/inorganic hybrid material. The POSS can be used as a good nano component to be introduced into a polymer system, so that the star-shaped hybrid spiral polyisonitrile prepared by designing and synthesizing an organic/inorganic hybrid material with a novel structure as a catalyst for polymerization has great potential application value.
Disclosure of Invention
The invention aims to: provides a cage type Polysilsesquioxane (POSS) based star-shaped hybrid spiral polyisonitrile and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
an organic/inorganic hybrid palladium catalyst, the structure of which is shown as the following general formula:
in the formula
A preparation method of an organic/inorganic hybrid palladium catalyst comprises the following steps:
a. dissolving octa-amino POSS and a reagent A in dichloromethane, adding a reagent B and triethylamine, reacting at room temperature for 22-25h in the atmosphere of nitrogen or argon, and stopping reaction; separating and taking an organic phase, washing, purifying, drying, evaporating to remove the solvent, adding dichloromethane, and precipitating with diethyl ether to obtain an intermediate I;
b. adding bis (triethylphosphine) palladium dichloride, cuprous chloride and an intermediate I into dichloromethane, adding triethylamine, stirring and reacting at room temperature for 2.5-3.5h under the atmosphere of nitrogen or argon, removing the solvent by rotary evaporation, purifying the crude product, and drying to obtain an organic/inorganic hybrid palladium catalyst;
wherein the structural formula of the intermediate I is as follows:
The reagent A is any one of propargyl alcohol ring-opening succinic anhydride, glutaric anhydride and adipic anhydride;
the reagent B is one or more of 1-hydroxybenzotriazole, O-benzotriazol-tetramethylurea hexafluorophosphate, 4-dimethylaminopyridine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and dicyclohexylcarbodiimide.
Preferably, when the reagent A is monopropynyl succinate and the reagent B is O-benzotriazole-tetramethyluronium hexafluorophosphate:
in the step a, the molar ratio of octamino POSS, monopropynyl succinate, O-benzotriazole-tetramethyluronium hexafluorophosphate to 1-hydroxybenzotriazole is 0.17: (4-8): 2.73: 2.73;
in the step b, the molar ratio of the bis (triethylphosphine) palladium dichloride, the cuprous chloride and the intermediate I is 2: 0.2: 0.25.
preferably, the organic phase is separated in step a, washed, purified, dried, the solvent is removed by evaporation, dichloromethane is added and the intermediate I is precipitated with diethyl ether in the following specific process: taking an organic phase by using dichloromethane, washing the organic phase by using a saturated ammonium chloride solution, a saturated sodium bicarbonate solution and a saturated sodium chloride solution for 3-4 times in sequence, adding anhydrous sodium sulfate for drying, evaporating to remove a solvent to obtain a crude product, dissolving the crude product by using dichloromethane, dropwise adding the crude product into frozen ether, and performing suction filtration to collect a solid intermediate I.
Preferably, the volume ratio of dichloromethane to frozen diethyl ether in step a is 1: 10.
Preferably, the specific processes of purification and drying in step b are as follows: purifying the crude product by silica gel column chromatography, and drying in vacuum to obtain a palladium catalyst, wherein the eluent is firstly mixed with petroleum ether and ethyl acetate, then is mixed with methanol, and the methanol solution is collected and dried by spinning; wherein the volume ratio of petroleum ether to ethyl acetate in the eluent is 1:1, the volume ratio of the mixture of the petroleum ether and the ethyl acetate to the methanol is 5: 3.
A cage type polysilsesquioxane base star-shaped hybridization spiral polyisonitrile has the following structural general formula:
wherein the polymerization degree m is 10-60;
a preparation method of cage-type polysilsesquioxane-based star-shaped hybrid spiral polyisonitrile comprises the following steps:
adding an organic/inorganic hybrid palladium catalyst and a phenylisonitrile monomer into a polymerization bottle, vacuumizing and filling nitrogen under the anhydrous and anaerobic conditions, adding a dry solvent tetrahydrofuran, performing reflux reaction at 55-60 ℃ for 20-24h, adding methanol to stop the reaction, washing the obtained product with methanol, and performing vacuum drying until the quality is unchanged to obtain a phenylisonitrile polymer;
wherein, the structural formula of the benzilonitrile monomer is as follows:
in the formula (I), the compound is shown in the specification,
preferably, the molar ratio of the organic/inorganic hybrid palladium catalyst to the benzilonitrile monomer is 1: (10-60), when the dosage of the phenyl isonitrile monomer is 30-100mg, the dosage of the solvent tetrahydrofuran is 1-3 mL.
The application of the cage polysilsesquioxane-based star-shaped hybrid spiral polyisonitrile can be used in the fields of functional polymer materials, drug carriers, nanotechnology, self-assembly, chiral separation, dye adsorption and intelligent materials.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the polyhedral oligomeric silsesquioxane (POSS) -based star-shaped hybrid spiral polyisonitrile is simple, has low requirements on experimental conditions, is convenient and fast to operate, and is easy to carry out reaction.
2. The star-shaped hybrid spiral polyisonitrile obtained by the organic/inorganic hybrid palladium catalyst has a more regular structure than a single-chain polymer, and has higher molecular weight and lower molecular weight distribution.
3. The invention combines organic materials and inorganic materials, and has great application value in the fields of self-assembly, drug loading, chiral separation, dye adsorption and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the organic/inorganic palladium catalyst in example 1 of the present invention, and it can be confirmed that the organic/inorganic palladium catalyst is obtained.
FIG. 2 shows a hand in embodiment 2 of the present inventionSex C10Gel permeation chromatograms of the isonitrile polymers can demonstrate that high molecular weight polymers are obtained.
FIG. 3 shows chirality C in example 2 of the present invention10The presence of chirality in the resulting polyisonitrile can be demonstrated by circular dichroism plots of the isonitrile polymers.
FIG. 4 shows chirality C in example 3 of the present invention10The critical micelle concentration of the isocyanate block three-arm hydrophilic isocyanate can prove that the obtained polyisonitrile can be self-assembled.
FIG. 5 shows chirality C in example 3 of the present invention10The dynamic light scattering pattern of the isocyanate block three-arm hydrophilic isocyanate can measure the particle size of the obtained polyisonitrile after self-assembly.
FIG. 6 shows chirality C in example 3 of the present invention10The appearance of the polyisonitrile after self-assembly can be observed from the atomic force microscope picture of the isonitrile block three-arm hydrophilic isonitrile.
Detailed Description
Example 1: preparation method of organic/inorganic hybrid palladium catalyst
a. 0.17mmol (0.20g) of octamino POSS and 4.09mmol (0.63g) of monopropynyl succinate were dissolved in 50mL of dichloromethane, and 2.73mmol (1.03g) of O-benzotriazol-tetramethyluronium hexafluorophosphate, 2.73mmol (0.37g) of 1-hydroxybenzotriazole and 10mL of triethylamine were added. The reaction was stopped by reacting at room temperature for 24 hours under a nitrogen atmosphere. The organic phase was taken with 30mL of dichloromethane, washed 3 times with saturated ammonium chloride solution, saturated sodium bicarbonate solution, and saturated sodium chloride solution in this order, dried by adding anhydrous sodium sulfate, and the solvent was removed by evaporation to give a crude product. Adding 2mL of dichloromethane and precipitating with 20mL of diethyl ether to obtain an intermediate I; the structural formula is as follows:
b. 2mmol (726.64mg) of bis (triethylphosphine) palladium dichloride, 0.2mmol (19.95mg) of cuprous chloride and 0.25mmol (500.00mg) of intermediate I were added to 10mL of dichloromethane, and another 10mL of triethylamine was added. Stirring and reacting for 3h at room temperature under the atmosphere of nitrogen, removing the solvent by rotary evaporation, purifying the crude product by silica gel column chromatography (50 mL of eluent is eluted by petroleum ether and ethyl acetate which are 1:1 in volume ratio and is eluted by 30mL of pure methanol), and drying in vacuum to obtain 200mg of yellow liquid, namely the palladium catalyst, wherein the structural formula of the palladium catalyst is as follows:
The synthetic route of the organic/inorganic hybrid palladium catalyst is as follows:
in the formula
Example 2: initiating chirality C10Isonitrile polymerization
Chiral C10The isonitrile polymerization was carried out under anhydrous and oxygen-free conditions, and 1.60mg (0.0003mmol) of the palladium catalyst prepared in example 1, chiral C, was charged into a 10mL polymerization flask1019.31mg (0.0614mmol) of isonitrile monomer, vacuumizing and charging nitrogen for 3 times, adding 1mL of dried tetrahydrofuran, refluxing at 55 ℃ for 8h, adding 10mL of methanol for quenching, precipitating the polymer, washing with methanol for 5 times, centrifuging to obtain yellow flocculent precipitate, and vacuum drying until the quality is unchanged.
The structural formula of the phenyl isonitrile monomer in the embodiment is as follows:
the structural formula of the obtained product is as follows:
example 3: chiral C10Isonitrile block three-arm hydrophilic isonitriles
15.2mg of the polymer prepared in example 2 and 139.81mg (0.19mmol) of three-armed hydrophilic isonitrile monomer are added into a 10mL polymerization bottle, the mixture is vacuumized and filled with nitrogen for 3 times, 0.8mL of dried tetrahydrofuran is added, after reflux reaction at 55 ℃ for 20 hours, 10mL of methanol is added for quenching, the polymer is precipitated and washed for 5 times by methanol, white flocculent precipitate is obtained by centrifugation, and the mass is dried in vacuum until the white flocculent precipitate is unchanged.
The structural formula of the phenyl isonitrile monomer in the embodiment is as follows:
the structural formula of the obtained product is as follows:
example 4: chiral C10Isonitrile block pentafluorophenol isonitrile
15.2mg of the polymer prepared in example 2 and 3.78mg (0.01mmol) of pentafluorophenol isonitrile monomer are added into a 10mL polymerization flask, the mixture is vacuumized and charged with nitrogen for 3 times, 0.8mL of dry tetrahydrofuran is added, after reflux reaction at 55 ℃ for 20 hours, 10mL of methanol is added for quenching, the polymer is precipitated and separated out, the mixture is washed with methanol for 5 times, white flocculent precipitate is obtained by centrifugation, and the mixture is dried in vacuum until the mass is unchanged.
The structural formula of the phenyl isonitrile monomer in the embodiment is as follows:
the structural formula of the obtained product is as follows:
the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed process flow, i.e. it is not meant to imply that the present invention must rely on the above detailed process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. An organic/inorganic hybrid palladium catalyst is characterized in that the structure of the catalyst is shown as the following general formula:
2. A method for preparing the organic/inorganic hybrid palladium catalyst according to claim 1, which comprises the following steps:
a. dissolving octa-amino POSS and a reagent A in dichloromethane, adding a reagent B and triethylamine, reacting at room temperature for 22-25h in the atmosphere of nitrogen or argon, and stopping reaction; separating and taking an organic phase, washing, purifying, drying, evaporating to remove the solvent, adding dichloromethane, and precipitating with diethyl ether to obtain an intermediate I;
b. adding bis (triethylphosphine) palladium dichloride, cuprous chloride and an intermediate I into dichloromethane, adding triethylamine, stirring and reacting at room temperature for 2.5-3.5h under the atmosphere of nitrogen or argon, removing the solvent by rotary evaporation, purifying the crude product, and drying to obtain an organic/inorganic hybrid palladium catalyst;
wherein the structural formula of the intermediate I is as follows:
The reagent A is any one of propargyl alcohol ring-opening succinic anhydride, glutaric anhydride and adipic anhydride;
the reagent B is one or more of 1-hydroxybenzotriazole, O-benzotriazol-tetramethylurea hexafluorophosphate, 4-dimethylaminopyridine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and dicyclohexylcarbodiimide.
3. The method for preparing an organic/inorganic hybrid palladium catalyst according to claim 2, wherein:
when the reagent A is monopropynyl succinate and the reagent B is O-benzotriazole-tetramethyluronium hexafluorophosphate:
in the step a, the molar ratio of octamino POSS, monopropynyl succinate, O-benzotriazole-tetramethyluronium hexafluorophosphate to 1-hydroxybenzotriazole is 0.17: (4-8): 2.73: 2.73;
in the step b, the molar ratio of the bis (triethylphosphine) palladium dichloride, the cuprous chloride and the intermediate I is 2: 0.2: 0.25.
4. the method for preparing an organic/inorganic hybrid palladium catalyst according to claim 2, wherein:
the specific process of separating and taking the organic phase in the step a, washing, purifying, drying, evaporating to remove the solvent, adding dichloromethane and precipitating with diethyl ether to obtain the intermediate I is as follows: taking an organic phase by using dichloromethane, washing the organic phase by using a saturated ammonium chloride solution, a saturated sodium bicarbonate solution and a saturated sodium chloride solution for 3-4 times in sequence, adding anhydrous sodium sulfate for drying, evaporating to remove a solvent to obtain a crude product, dissolving the crude product by using dichloromethane, dropwise adding the crude product into frozen ether, and performing suction filtration to collect a solid intermediate I.
5. The method for preparing an organic/inorganic hybrid palladium catalyst according to claim 4, wherein:
the volume ratio of dichloromethane to frozen diethyl ether in step a was 1: 10.
6. The method for preparing an organic/inorganic hybrid palladium catalyst according to claim 2, wherein:
the specific process of purification and drying in the step b is as follows: purifying the crude product by silica gel column chromatography, and drying in vacuum to obtain a palladium catalyst, wherein the eluent is firstly mixed with petroleum ether and ethyl acetate, then is mixed with methanol, and the methanol solution is collected and dried by spinning; wherein the volume ratio of petroleum ether to ethyl acetate in the eluent is 1:1, the volume ratio of the mixture of the petroleum ether and the ethyl acetate to the methanol is 5: 3.
7. A cage type polysilsesquioxane base star hybridization spiral polyisonitrile is characterized in that: the general structural formula is as follows:
wherein the polymerization degree m is 10-60;
8. a method for preparing the cage-type polysilsesquioxane-based star hybrid helical polyisonitrile of claim 7, wherein: the method comprises the following specific steps:
adding an organic/inorganic hybrid palladium catalyst and a phenylisonitrile monomer into a polymerization bottle, vacuumizing and filling nitrogen under the anhydrous and anaerobic conditions, adding a dry solvent tetrahydrofuran, performing reflux reaction at 55-60 ℃ for 20-24h, adding methanol to stop the reaction, washing the obtained product with methanol, and performing vacuum drying until the quality is unchanged to obtain a phenylisonitrile polymer;
wherein, the structural formula of the benzilonitrile monomer is as follows:
in the formula (I), the compound is shown in the specification,
9. the method for preparing the cage-type polysilsesquioxane-based star hybrid helical polyisonitrile as recited in claim 8, wherein: the molar ratio of the organic/inorganic hybrid palladium catalyst to the benzene isonitrile monomer is 1: (10-60), when the dosage of the phenyl isonitrile monomer is 30-100mg, the dosage of the solvent tetrahydrofuran is 1-3 mL.
10. Use of the cage polysilsesquioxane based star hybrid helical polyisonitrile of claim 7, wherein: can be used in the fields of functional polymer materials, drug carriers, nanotechnology, self-assembly, chiral separation, dye adsorption and intelligent materials.
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| CN113061210A (en) * | 2021-03-26 | 2021-07-02 | 合肥工业大学 | Janus type star polymer with circular polarization fluorescence |
| CN114621417A (en) * | 2022-03-28 | 2022-06-14 | 合肥工业大学 | Optically active spiral polyfluorene block polyisonitrile copolymer and preparation method and application thereof |
| CN114621417B (en) * | 2022-03-28 | 2024-04-09 | 合肥工业大学 | Optically active spiral polyfluorene block polyisonitrile copolymer and preparation method and application thereof |
| CN114989426B (en) * | 2022-06-20 | 2024-03-15 | 合肥工业大学 | Polymer brush of poly (isonitrile) grafted polyoxazoline and preparation method thereof |
| CN116143134A (en) * | 2023-02-17 | 2023-05-23 | 江苏海格新材料有限公司 | Preparation method of silicon micropowder for integrated circuit packaging |
| CN116143134B (en) * | 2023-02-17 | 2023-10-20 | 江苏海格新材料有限公司 | Preparation method of silicon micropowder for integrated circuit packaging |
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