CN111621020B - Giant surfactant and preparation method thereof - Google Patents

Giant surfactant and preparation method thereof Download PDF

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CN111621020B
CN111621020B CN202010385766.1A CN202010385766A CN111621020B CN 111621020 B CN111621020 B CN 111621020B CN 202010385766 A CN202010385766 A CN 202010385766A CN 111621020 B CN111621020 B CN 111621020B
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张昕玥
董学会
甘展慧
周冬冬
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South China University of Technology SCUT
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Abstract

The invention discloses a giant surfactant and a preparation method thereof. The preparation method of the giant surfactant with the tail chain being the single-chain nano-particle comprises the following steps: 1) performing cycloaddition reaction on linear poly (styrene-r-benzocyclobutene) containing hydroxyl to initiate intramolecular crosslinking to prepare single-chain nano particles containing hydroxyl; 2) carrying out nucleophilic substitution reaction on the hydroxyl-containing single-chain nanoparticles, and then carrying out azide reaction to prepare single-chain nanoparticles containing azide groups; 3) carrying out azide-alkyne click chemical reaction on single-chain nanoparticles containing azide groups and mono-alkynyl heptavinyl polyhedral oligomeric silsesquioxane to prepare the polyhedral oligomeric silsesquioxane containing the single-chain nanoparticles; 4) the polyhedral oligomeric silsesquioxane containing the single-chain nanoparticles is prepared by a sulfydryl-double bond click chemical reaction. The giant surfactant has a novel tail topological structure, and the preparation method has the characteristics of simple operation, high reaction efficiency and large-scale preparation.

Description

Giant surfactant and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a giant surfactant with a single-chain nanoparticle tail chain and a preparation method thereof.
Background
The giant surfactant is an amphiphilic molecule formed by connecting a functionalized nano atom head group and a polymer tail chain through a covalent bond. "nanoatoms" are a class of caged molecules with precise chemical structure, nanometer size and rigid three-dimensional framework. Typical nanoparticles include polyhedral oligomeric silsesquioxanes (POSS), fullerenes (e.g., C)60) And derivatives of metallo-heteropoly acids (POMs), and the like. Giant surfactants are similar in molecular shape to small molecule surfactants, but are scaled up in size to the polymer level. Since the concept is provided, the giant surfactant shows abundant self-assembly behaviors in both bulk and solution, draws the attention of academia, and has wide potential application in the fields of energy, catalysis, biomedical engineering and the like.
Compared with traditional amphiphilic polymers based on flexible macromolecular chains, the 'nano-atoms' with relatively rigid molecular conformation can remarkably amplify the topological structure effect of the giant surfactant. Meanwhile, researches find that the tail chain topology of the giant surfactant has a decisive influence on the self-assembly behavior, but how to synthesize tail chains with rich topology still lacks sufficient exploration.
Polyhedral oligomeric silsesquioxane (POSS) is a nano atom with a molecular framework formed by alternately connecting silicon and oxygen (Si-O), and a giant surfactant can obtain a synergistic secondary bond effect by densely introducing a plurality of functional groups at the top of POSS, so that the apparent χ value between the nano atom and a high molecular chain is remarkably increased to adjust the driving force of microphase separation.
Single-chain nanoparticles (SCNPs) are particulate polymers formed by intramolecular entanglement folding of a single polymer chain by intramolecular chemical bonds. By adjusting the ratio of crosslinkable groups to polymer chains, the size of SCNPs can be precisely controlled. Compared with linear polymer precursors, SCNPs have the characteristics of smaller hydrodynamic volume, higher glass transition temperature, and lower solution viscosity.
Disclosure of Invention
In the prior art, the giant surfactant with the tail chain being SCNP and the preparation method thereof are not reported. Therefore, an object of the present invention is to provide a giant surfactant with a single-stranded tail, a second object of the present invention is to provide a method for preparing the giant surfactant with a single-stranded tail, and a third object of the present invention is to provide an application of the giant surfactant.
The inventor finds that: the SCNP tail chain is connected with the POSS head group, so that the giant surfactant with richer topological structure can be prepared, and the special assembly behavior caused by the topological effect can be obtained.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a giant surfactant with a single-chain tail chain as a nano particle.
A giant surfactant has a structural formula shown as a formula (I):
Figure BDA0002483745820000021
in the formula (I), R1Denotes linear poly (styrene-R-benzocyclobutene) intramolecular cross-linking, R2Represents a hydrophilic group; m is the number of styrene monomers in a single molecule, n is the number of benzocyclobutene monomers in a single molecule, m: n is (2-9): 1.
in the formula (I), m and n are positive integers.
Further, in the formula (I), R1Shown is an intramolecular cross-linked structure formed by benzocyclobutene cycloaddition reaction of linear poly (styrene-r-benzocyclobutene). The polymer chains of these intramolecular cross-linking moieties are not linear, but rather groups are present in the chain segments which are linked to one another, the linked group being R1The adjacent ring structure, the whole molecule is similar to a winding ball.
Preferably, in formula (I), R2Is selected from C2～C6A straight or branched alkyl alcohol of (C)2～C6Linear or branched polyol, benzyl alcohol, C2～C6One or more of linear or branched carboxylic acids of (a); further preferably, R2Is selected from C2～C3Straight alkanols, C3～C4Branched alkanol, C3～C4Straight chain polyol, C3～C4Branched polyol, C2～C3One or more of linear carboxylic acids; even more preferably, R2Is selected from C2Straight alkanols, C3Straight chain polyol, C2One or more of linear carboxylic acids.
The invention also provides a preparation method of the giant surfactant. The preparation of the giant surfactant with the tail chain being the single-chain nano-particle comprises the following steps: 1) constructing single-chain nano particles by using a linear polymer containing a cross-linkable functional group; 2) nitridizing the single-chain nano particles; 3) connecting the single-chain nano particles with the polyhedral oligomeric silsesquioxane through a click chemical reaction; 4) and (3) functional modification of polyhedral oligomeric silsesquioxane. The following further illustrates the preparation of the giant surfactant of formula (I):
a preparation method of a giant surfactant comprises the following steps:
1) linear poly (styrene-r-benzocyclobutene) (P (S-r-bcbS) -OH) containing hydroxyl is subjected to cycloaddition reaction of benzocyclobutene to initiate intramolecular crosslinking to prepare single-chain nano particles (SCNP P (S-r-bcbS) -OH) containing hydroxyl;
2) the hydroxyl-containing single-chain nano-particle is subjected to nucleophilic substitution reaction of acyl halide and hydroxyl to prepare an acyl halide group-containing single-chain nano-particle (SCNP P (S-r-bcbS) -X, wherein X is selected from F, Cl, Br or I), and then subjected to azide reaction to prepare an azide group-containing single-chain nano-particle (SCNP P (S-r-bcbS) -N3)；
3) Carrying out azide-alkyne click chemical reaction on single-chain nanoparticles containing azide groups and monoalkynyl heptavinyl polyhedral oligomeric silsesquioxane (VPOSS-alkyne) to prepare the polyhedral oligomeric silsesquioxane (SCNP VPOSS-P (S-r-bcbS) -N containing the single-chain nanoparticles3)；
4) The polyhedral oligomeric silsesquioxane containing single-chain nanoparticles is subjected to sulfydryl-double bond click chemical reaction to prepare the giant surfactant with the tail chain being the single-chain nanoparticles.
Preferably, in step 1) of the preparation method of the giant surfactant, the cycloaddition reaction specifically comprises: and (2) dropwise adding the hydroxyl-containing linear poly (styrene-r-benzocyclobutene) solution into an organic solvent, and heating for reaction to obtain the hydroxyl-containing single-chain nano particle.
Preferably, in the step 1) of the preparation method of the giant surfactant, the used organic solvent is a solvent with the boiling point being more than or equal to 280 ℃; further preferably, the solvent used in step 1) is benzyl ether.
Preferably, in the step 1) of the preparation method of the giant surfactant, the dropping speed of the hydroxyl-containing linear poly (styrene-r-benzocyclobutene) solution is 150 to 250 mu L/min; further preferably, the dropping speed of the hydroxyl group-containing linear poly (styrene-r-benzocyclobutene) solution is 150 to 220. mu.L/min.
Preferably, in step 1) of the method for preparing the giant surfactant, the solution of the hydroxyl group-containing linear poly (styrene-r-benzocyclobutene) is a dibenzyl ether solution of the hydroxyl group-containing linear poly (styrene-r-benzocyclobutene).
Preferably, in the step 1) of the preparation method of the giant surfactant, the concentration of the hydroxyl-containing linear poly (styrene-r-benzocyclobutene) solution is 4 mg/mL-10 mg/mL; further preferably, the concentration of the hydroxyl group-containing linear poly (styrene-r-benzocyclobutene) solution is 5mg/mL to 6.25 mg/mL.
Preferably, in step 1) of the preparation method of the giant surfactant, the volume ratio of the hydroxyl-containing linear poly (styrene-r-benzocyclobutene) solution to the organic solvent is 1: (8-13).
Preferably, in step 1) of the preparation method of the giant surfactant, the reaction temperature is 240-260 ℃.
Preferably, in the step 1) of the preparation method of the giant surfactant, the reaction time is 1-5 h; more preferably, the reaction time is 2 to 3 hours.
In some preferred embodiments of the present invention, the cycloaddition reaction of step 1) is: dripping the dibenzyl ether solution of the linear poly (styrene-r-benzocyclobutene) containing hydroxyl into the dibenzyl ether stirred at the temperature of 240-260 ℃, and continuously stirring and reacting for 2-3 h at the temperature of 240-260 ℃ after dripping to obtain the single-chain nano particles containing hydroxyl.
Preferably, in step 1) of the preparation method of the giant surfactant, the structural formula of the hydroxyl-containing linear poly (styrene-r-benzocyclobutene) is shown as the formula (II):
Figure BDA0002483745820000041
in formula (ii), m is the number of styrene monomers in a single molecule, n is the number of benzocyclobutene monomers in a single molecule, m: n is (2-9): 1;
the structural formula of the hydroxyl-containing single-chain nano particle is shown as the formula (III):
Figure BDA0002483745820000042
in formula (iii), m is the number of styrene monomers in a single molecule, n is the number of benzocyclobutene monomers in a single molecule, m: n is (2-9): 1; r1Represents linear poly (styrene-r-benzocyclobutene) intramolecular crosslinks containing hydroxyl groups.
M and n in the formulas (II) and (III) are the same as m and n in the formula (I), and R in the formula (III)1Has the meaning of R in formula (I)1The same is true.
The molecular structures of formula (I), (II) and (III) are shown in figure 1.
Preferably, in the step 1), the hydroxyl-containing linear poly (styrene-r-benzocyclobutene) has a relative molecular mass of 2000g/mol to 8000 g/mol; more preferably, the hydroxyl group-containing linear poly (styrene-r-benzocyclobutene) has a relative molecular mass of 2600g/mol to 6400 g/mol.
Preferably, in step 2) of the preparation method of the giant surfactant, the nucleophilic substitution reaction specifically comprises: dissolving the hydroxyl-containing single-chain nano-particles in an organic solvent, adding an alkaline catalyst, and then adding acyl halide to react to obtain the acyl halide-group-containing single-chain nano-particles.
Preferably, in the nucleophilic substitution reaction in the step 2), the concentration of the hydroxyl-containing single-chain nanoparticles in the organic solvent is 50 mg/mL-80 mg/mL; more preferably, the concentration of the hydroxyl group-containing single-stranded nanoparticles in the organic solvent is 55mg/mL to 65 mg/mL.
Preferably, in the nucleophilic substitution reaction of step 2), the molar ratio of the hydroxyl-containing single-chain nanoparticle, the basic catalyst and the acyl halide is 1: (4-6): (5-15).
Preferably, in the nucleophilic substitution reaction of step 2), the organic solvent is a halogenated hydrocarbon solvent; further preferably, in the nucleophilic substitution reaction in step 2), the organic solvent is at least one selected from dichloromethane and chloroform.
In the nucleophilic substitution reaction in the step 2), the alkaline catalyst is a weakly alkaline catalyst; preferably, the basic catalyst is selected from at least one of pyridine, triethylamine, and 4-Dimethylaminopyridine (DMAP).
Preferably, in the nucleophilic substitution reaction in the step 2), the acyl halide is added dropwise; the preferable speed of the acid halide is 20 to 50. mu.L/min, and more preferably 30 to 40. mu.L/min.
Preferably, in the nucleophilic substitution reaction of step 2), the acyl halide is acyl bromide; further preferably, the acid halide is 2-bromoisobutyryl bromide. When the selected acyl halide is acyl bromide, the single-chain nano-particle containing the acyl halide group prepared by the nucleophilic substitution reaction is the single-chain nano-particle containing the acyl bromide group (SCNP P (S-r-bcbS) -Br).
Preferably, the nucleophilic substitution reaction of step 2) is carried out under stirring at normal temperature; the stirring reaction time is preferably 12 to 24 hours.
In some preferred embodiments of the present invention, the nucleophilic substitution reaction of step 2) is: dissolving the hydroxyl-containing single-chain nano-particles in dichloromethane, adding pyridine, dropwise adding acyl halide at 0 ℃, and stirring at normal temperature for reaction to obtain the acyl halide-group-containing single-chain nano-particles.
Preferably, in step 2) of the preparation method of the giant surfactant, the azide reaction specifically comprises: dissolving the single-chain nano-particles containing acyl halide groups in an organic solvent, adding an azide reagent, and reacting to obtain the single-chain nano-particles containing the azide groups.
Preferably, in the azide reaction in the step 2), the concentration of the single-chain nanoparticles containing acyl halide groups in the organic solvent is 40mg/mL to 70 mg/mL.
Preferably, in the nitridizing reaction of the step 2), the molar ratio of the single-chain nano-particle containing acyl halide group to the nitridizing reagent is 1: (5-10).
Preferably, in the azide reaction in the step 2), the organic solvent is at least one selected from the group consisting of N, N-dimethylformamide, tetrahydrofuran, dimethyl sulfoxide and acetone; further preferably, the organic solvent is N, N-dimethylformamide. The amount of the organic solvent is such that the single-chain nanoparticles containing the acyl halide group are dissolved.
Preferably, in the nitridization reaction in the step 2), the nitridizing reagent is at least one selected from sodium azide and diphenylphosphoryl azide.
Preferably, the azide reaction in step 2) is a reaction with stirring at normal temperature.
In some preferred embodiments of the invention, the azide reaction of step 2) is: dissolving the single-chain nano-particles containing acyl halide groups into N, N-dimethylformamide, adding sodium azide, and stirring at normal temperature to react to obtain the single-chain nano-particles containing the azide groups.
Preferably, in step 3) of the preparation method of the giant surfactant, the azide-alkyne click chemistry reaction is specifically as follows: dissolving single-chain nanoparticles containing azide groups in an organic solvent, adding monoalkynyl heptavinyl polyhedral oligomeric silsesquioxane, cuprous salt and a ligand to react to obtain the polyhedral oligomeric silsesquioxane containing the single-chain nanoparticles; further preferably, the azide-alkyne click chemistry reaction is specifically: dissolving single-chain nanoparticles containing azide groups in an organic solvent, adding monoalkynyl heptavinyl polyhedral oligomeric silsesquioxane and cuprous salt, removing oxygen from the system, adding a ligand in an inert atmosphere, and stirring for reaction to obtain the polyhedral oligomeric silsesquioxane containing single-chain nanoparticles.
Preferably, in the azide-alkyne click chemistry reaction in the step 3), the mole ratio of the single-chain nanoparticles containing azide groups, the monoalkynyl heptavinyl polyhedral oligomeric silsesquioxane, the cuprous salt and the ligand is 1: (1.2-2): (1-5): (1-5).
Preferably, in the azide-alkyne click chemistry reaction in the step 3), the concentration of the single-chain nanoparticles containing azide groups in the organic solvent is 50-100 mg/mL.
Preferably, in the azide-alkyne click chemistry reaction in the step 3), the organic solvent is at least one selected from benzene solvents, ester solvents, ether solvents, ketone solvents and alcohol solvents; further preferably, the organic solvent is at least one selected from the group consisting of toluene, xylene, and ethylbenzene.
Preferably, in the azide-alkyne click chemistry reaction in the step 3), the cuprous salt is at least one selected from cuprous bromide, cuprous chloride and cuprous iodide; more preferably, the cuprous salt is cuprous bromide.
Preferably, in the azide-alkyne click chemistry reaction of the step 3), the ligand is at least one selected from the group consisting of N, N ', N ″ -Pentamethyldiethylenetriamine (PMDETA), 2' -bipyridine, tris (2-dimethylaminoethyl) amine, tripropylene glycol methyl ether acetate; more preferably, the ligand is N, N', N ″ -pentamethyldiethylenetriamine. The ligand is complexed with cuprous salt to play a catalytic role.
Preferably, in the azide-alkyne click chemistry reaction in the step 3), the gas of the inert atmosphere is selected from at least one of nitrogen and helium; further preferably, the inert gas atmosphere is a nitrogen gas atmosphere.
Preferably, in the azide-alkyne click chemical reaction in the step 3), the reaction time is 10-24 h; more preferably, the reaction time is 12 to 24 hours.
Preferably, the azide-alkyne click chemistry of step 3) is carried out at ambient temperature.
Preferably, in the step 3) of the preparation method of the giant surfactant, the structural formula of the monoalkynyl heptavinyl polyhedral oligomeric silsesquioxane is shown as a formula (IV):
Figure BDA0002483745820000061
preferably, in step 4) of the preparation method of the giant surfactant, the thiol-double bond click chemistry reaction specifically comprises: the polyhedral oligomeric silsesquioxane containing single-chain nanoparticles is dissolved in an organic solvent, a thiol compound containing hydroxyl and a photoinitiator are added, and the reaction is carried out under the illumination to obtain the giant surfactant with the tail chain being the single-chain nanoparticles.
Preferably, in the thiol-double bond click chemistry reaction of step 4), the concentration of the polyhedral oligomeric silsesquioxane containing single-chain nanoparticles in the organic solvent is 50mg/mL to 200 mg/mL.
Preferably, in the thiol-double bond click chemistry reaction of step 4), the organic solvent is at least one selected from tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, and acetone.
Preferably, in the thiol-double bond click chemistry reaction of step 4), the molar ratio of the polyhedral oligomeric silsesquioxane containing single-chain nanoparticles, the thiol compound containing hydroxyl groups, and the photoinitiator is 1: (42-63): (0.2-2).
Preferably, in the thiol-double bond click chemistry reaction of the step 4), the thiol compound having a hydroxyl group is selected from at least one of 3-mercapto-1, 2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, 3-mercapto-2-methyl-1-pentanol, 3-mercapto-1-hexanol, 2-mercaptoethanol, 3-mercaptopropanol, 4-mercapto-1-butanol, 6-mercaptohex-1-ol, 2-mercaptobenzyl alcohol, 4-mercaptobenzyl alcohol, 2-mercaptoacetic acid, 3-mercaptopropionic acid, 2, 3-dimercaptomalonic acid; further preferably, the hydroxyl group-containing thiol compound is at least one selected from the group consisting of 3-mercapto-1, 2-propanediol, 2-mercaptoethanol, and 2-mercaptoacetic acid.
Preferably, in the mercapto-double bond click chemistry reaction of the step 4), the photoinitiator is at least one selected from 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 1-hydroxycyclohexyl phenyl ketone and methyl benzoylformate; further preferably, the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone.
Preferably, in the mercapto-double bond click chemistry reaction in the step 4), the illumination is ultraviolet illumination; the time of illumination is preferably 10min to 40 min; the ultraviolet wavelength is preferably 365 nm.
Preferably, the thiol-double bond click chemistry reaction of step 4) is performed at normal temperature.
In some preferred embodiments of the present invention, the thiol-double bond click chemistry reaction of step 4) is: the polyhedral oligomeric silsesquioxane containing single-chain nanoparticles is dissolved in tetrahydrofuran, a thiol compound containing hydroxyl and a photoinitiator are added, and stirring reaction is carried out under ultraviolet illumination to obtain the giant surfactant with the tail chain being the single-chain nanoparticles.
Preferably, after any one of the reactions of step 1), step 2), step 3) and step 4), the method further comprises a step of purifying the product; the purity of the product is improved by purification and separation, wherein the purification step comprises but is not limited to chromatography, extraction method, dissolution precipitation separation method, filtration method, reduced pressure distillation method and the like.
The invention also provides the application of the giant surfactant in the fields of energy, catalysis or biomedical engineering.
The invention has the beneficial effects that:
compared with the traditional linear giant surfactant, the giant surfactant with a series of single-chain tail chains disclosed by the invention has a novel tail topological structure. The preparation method of the giant surfactant provided by the invention has the characteristics of simple operation, high reaction efficiency and large-scale preparation.
Specifically, compared with the prior art, the invention has the following advantages:
1) the invention successfully constructs the giant surfactant with the tail chain of a novel topological structure, and has wide potential application in the fields of energy, catalysis, biomedical engineering and the like;
2) the tail chain of the giant surfactant prepared by the invention is a single-chain nano particle, and the head part of the giant surfactant is polyhedral oligomeric silsesquioxane containing one or more different functional groups, so that richer self-assembly behaviors can be represented;
3) the preparation method has the characteristics of simple operation, high reaction efficiency and large-scale preparation.
Drawings
FIG. 1 is a schematic diagram of the molecular structures of formula (I), (II) and (III);
FIG. 2 is a schematic diagram of the reaction scheme for preparing the giant surfactant according to example 1 of the present invention;
FIG. 3 shows the NMR spectrum of the giant surfactant prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or equipment used in the examples are, unless otherwise specified, either conventionally commercially available or may be obtained by methods known in the art. Unless otherwise indicated, the testing or testing methods are conventional in the art.
Example 1
FIG. 2 is a schematic representation of the reaction scheme for the preparation of the giant surfactant of example 1. Referring to fig. 2, the method for preparing the giant surfactant of this example comprises the following steps:
step 1: the raw material is linear poly (styrene-r-benzocyclobutene) (P (S-r-bcbS) -OH) with hydroxyl, the relative molecular mass is 2600g/mol, and M: n is 9: 1. 250mL of dibenzyl ether was charged into a 500mL three-necked round-bottomed flask, and the flask was heated to 250 ℃ with stirring, and 200mg (0.077mmol) of P (S-r-bcbS) -OH was sufficiently dissolved in 40mL of dibenzyl ether, and the solution was added dropwise to the heated dibenzyl ether with a syringe pump at a rate of 150. mu.L/min. The whole process is vigorously stirred to ensure that the liquid is fully mixed, and after the dropwise addition is finished, the reactants are continuously heated and reacted for 2 hours at 250 ℃. After completion of the reaction, the benzyl ether solvent was removed by distillation under reduced pressure. The product was dissolved in 1mL of dichloromethane, precipitated dropwise into 30mL of methanol, filtered off the liquid by suction, and purified by repeated precipitation three times. After drying in a vacuum drying oven, the product was obtained as a white powder: hydroxyl group-containing single-chain nanoparticle (SCNP P (S-r-bcbS) -OH)190mg, yield: 95 percent.
Step 2: 600mg (0.231mmol) of SCNP P (S-r-bcbS) -OH obtained in step 1 was dissolved in 10mL of anhydrous dichloromethane in a single-neck round-bottom flask, 74.8mg (0.947mmol) of pyridine was added, stirring was performed at 0 ℃ in an ice bath, after the solvent was completely cooled, 214. mu.L (398mg, 1.73mmol) of 2-bromoisobutyryl bromide was added dropwise at a rate of 35. mu.L/min, and after the addition, the reaction was stirred at room temperature for 24 hours. After the reaction is finished, transferring the solvent into a separating funnel, adding 40mL of dichloromethane for dilution, repeatedly extracting with 100mL of deionized water for three times to remove unreacted small molecular substances, after the extraction is finished, adding anhydrous sodium sulfate into the solution for dewatering, performing suction filtration to remove insoluble anhydrous sodium sulfate, performing rotary evaporator to spin dry the solvent, fully dissolving the product with 2mL of dichloromethane, dropwise adding the product into 60mL of methanol for precipitation, finally performing suction filtration to remove liquid, and drying in a vacuum drying oven to obtain a white powdery product: 588mg of single-chain nanoparticles containing an acyl bromide group (SCNP P (S-r-bcbS) -Br), yield: 98 percent.
The obtained SCNP P (S-r-bcbS) -Br was dissolved in 10mL of N, N-Dimethylformamide (DMF) in a single-neck round-bottom flask, and 120.1mg (1.846mmol) of sodium azide was added thereto, followed by reaction with stirring at room temperature for 24 hours. After the reaction is finished, 150mL of deionized water is directly added into the solution for washing, the product can be separated out as an insoluble substance, meanwhile, redundant sodium azide is washed away, the washing is repeated for three times, the liquid is removed by suction filtration, and the white powdery product is obtained after the drying in a vacuum drying oven: single-chain nanoparticles with azido groups (SCNP P (S-r-bcbS) -N3)577mg, yield: 98 percent.
And step 3: 400mg (0.154mmol) of the SCNP P (S-r-bcbS) -N from step 23In a 50mL Schlenk solvent storage bottle, 5mL of toluene was dissolved, and 183mg (0.231mmol) of VPOSS-alkyne and 42.9mg (0.192mmol) of cuprous bromide were added. And (3) freezing and exhausting the reaction device for three times on a vacuum double-row pipe, discharging oxygen in the system, opening a Schlenk bottle under the condition of continuously introducing nitrogen, quickly adding 51.9mg of PMDETA, vacuumizing the system after sealing, finally unfreezing the solution, and stirring at normal temperature for reaction for 12 hours. After completion of the reaction the solution was transferred directly into a silica gel column and washed with the eluent dichloromethane: the petroleum ether (2:1) mixed solvent is firstly used for flushing unreacted raw materials with the minimum polarity, and then the eluent dichloromethane is used for: the product was collected by filtration with a mixture of solvents of methanol (9:1), the solvent was dried by spinning, the product was dissolved in 2mL of dichloromethane and then precipitated in 60mL of methanol, the liquid was removed by suction filtration and dried in a vacuum oven to give the product as a white powder: polyhedral oligomeric silsesquioxane (SCNP VPOSS-P (S-r-bcbS)) with single-chain nanoparticles as tails 248mg, yield: 62 percent.
And 4, step 4: 100mg (0.028mmol) of VPOSS-P (S-r-bcbS) obtained in step 3 was dissolved in 1mL of tetrahydrofuran in a 20mL transparent glass bottle, 172mg (1.592mmol) of 3-mercapto-1, 2-propanediol was added thereto and mixed with stirring, and 2mg (0.0149mmol) of 2, 2-dimethoxy-2-phenylacetophenone (DMPA) was added thereto and the mixture was irradiated with light under a 365nm ultraviolet lamp for 10min with stirring under irradiation. After the reaction is finished, directly dropwise adding the solution into 30mL of methanol for precipitation, centrifuging the precipitated turbid solution on a centrifuge at the speed of 10000r/min, pouring out the supernatant after the centrifugation is finished, dissolving the precipitate with 2mL of tetrahydrofuran, precipitating in the methanol, centrifuging again, and repeatedly purifying for three times to obtain a final product: tail chain single-chain nanoparticle giant surfactant (SCNP DPOSS-P (S-r-bcbS))86mg, yield: 86 percent.
FIG. 3 is a NMR spectrum of the giant surfactant prepared in this example.
Example 2
The method for preparing the giant surfactant comprises the following steps:
step 1: the raw material is linear poly (styrene-r-benzocyclobutene) (P (S-r-bcbS) -OH) with hydroxyl, the relative molecular mass is 4800g/mol, and M: n is 2.3: 1. 250mL of dibenzyl ether was added to a 500mL three-necked round-bottomed flask, and the flask was heated to 250 ℃ with stirring, and 250mg (0.052mmol) of P (S-r-bcbS) -OH was dissolved sufficiently in 40mL of dibenzyl ether, and this solution was added dropwise to the heated dibenzyl ether by means of a syringe pump at a rate of 200. mu.L/min, and vigorously stirred throughout the entire process to ensure sufficient mixing of the liquids, and after completion of the addition, the reaction mixture was further heated at 250 ℃ for 2 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, the product was dissolved in 1.5mL of methylene chloride, precipitated by dropping into 40mL of methanol, the solution was removed by suction filtration, and the precipitation and purification were repeated three times. After drying in a vacuum drying oven, the product was obtained as a white powder: single-stranded nanoparticles (SCNP P (S-r-bcbS) -OH)230mg, yield 92%.
Step 2: 600mg (0.125mmol) of SCNP P (S-r-bcbS) -OH obtained in step 1 was dissolved in 10mL of anhydrous dichloromethane in a single-neck round-bottom flask, 40.6mg (0.514mmol) of pyridine was added, stirring was performed at 0 ℃ in an ice bath, after the solvent was completely cooled, 157. mu.L (292mg, 1.26mmol) of 2-bromoisobutyryl bromide was added dropwise at a rate of 35. mu.L/min, and after the addition, the reaction was stirred at room temperature for 24 hours. After the reaction is finished, transferring the solvent into a separating funnel, adding 40mL of dichloromethane for dilution, repeatedly extracting with 100mL of deionized water for three times to remove unreacted small molecular substances, after the extraction is finished, adding anhydrous sodium sulfate into the solution for dewatering, performing suction filtration to remove the anhydrous sodium sulfate, performing rotary evaporator to spin dry the solvent, fully dissolving the product with 2mL of dichloromethane, dropwise adding the product into 60mL of methanol for precipitation, finally performing suction filtration to remove liquid, and drying in a vacuum drying oven to obtain a white powdery product: 582mg of single-chain nanoparticle containing a group of acyl bromide (SCNP P (S-r-bcbS) -Br) was obtained in a yield of 97%.
SCNP P (S-r-bcbS) -Br was dissolved in 10mL of N, N-Dimethylformamide (DMF) in a single-necked round-bottomed flask, and 33.9mg (0.522mmol) of sodium azide was added. The reaction is stirred at normal temperature for 24 hours. After the reaction is finished, 150mL of deionized water is directly added into the solution for washing, the product can be separated out as an insoluble substance, meanwhile, redundant sodium azide is washed away, the washing is repeated for three times, the liquid is removed by suction filtration, and the white powdery product is obtained after the drying in a vacuum drying oven: single-chain nanoparticles with azido groups (SCNP P (S-r-bcbS) -N3)570mg, yield 98%.
And step 3: 400mg of SCNP P (S-r-bcbS) -N from step 2 were added3(0.083mmol) was dissolved in 5mL toluene in a 50mL Schlenk solvent storage bottle, 85.8mg (0.108mmol) of VPOSS-alkyne and 37.2mg (0.167mmol) of cuprous bromide were added, the reaction apparatus was evacuated by freezing three times on a vacuum double-row tube, oxygen in the system was removed, the Schlenk bottle was opened under continuous nitrogen gas introduction, 28.8mg (0.166mmol) of PMDETA was rapidly added, the system was evacuated after sealing, and finally the solution was thawed and stirred at room temperature for 12 h. After completion of the reaction the solution was transferred directly into a silica gel column and washed with the eluent dichloromethane: the petroleum ether (2:1) mixed solvent is firstly used for flushing unreacted raw materials with the minimum polarity, and then the eluent dichloromethane is used for: the product was collected by filtration with a mixture of solvents of methanol (9:1), the solvent was dried by spinning, the product was dissolved in 2mL of dichloromethane and then precipitated in 60mL of methanol, and the liquid was removed by suction filtration. After drying in a vacuum drying oven, the product was obtained as a white powder: the tail chain is 236mg of polyhedral oligomeric silsesquioxane (SCNP VPOSS-P (S-r-bcbS)) with single-chain nanoparticles, and the yield is 59%.
And 4, step 4: 100mg (0.017mmol) of VPOSS-P (S-r-bcbS) obtained in step 3 was dissolved in 1mL of tetrahydrofuran in a 20mL transparent glass bottle, 78.0mg (1mmol) of 2-mercaptoethanol was added thereto, and the mixture was stirred, 2mg (0.0149mmol) of 2, 2-dimethoxy-2-phenylacetophenone (DMPA) was added thereto, and the mixture was irradiated with ultraviolet light at 365nm for 10 minutes while stirring. After the reaction is finished, directly dropwise adding the solution into 30mL of methanol for precipitation, centrifuging the precipitated turbid solution on a centrifuge at the speed of 10000r/min, pouring out the supernatant after the centrifugation is finished, dissolving the precipitate with 2mL of tetrahydrofuran, precipitating in the methanol, centrifuging again, and repeatedly purifying for three times to finally obtain a product: 82mg of the giant surfactant with single-stranded nanoparticle tail chain (SCNP HPOSS-P (S-r-bcbS)) was obtained in 82% yield.
Example 3
The method for preparing the giant surfactant comprises the following steps:
step 1: the raw material is linear poly (styrene-r-benzocyclobutene) (P (S-r-bcbS) -OH) with hydroxyl, the relative molecular mass is 6400g/mol, and M: n is 9: 1. 250mL of benzyl ether was added to a 500mL three-necked round-bottomed flask, heated to 250 ℃ with stirring, and 250mg of P (S-r-bcbS) -OH was dissolved sufficiently in 40mL of benzyl ether, and the solution was added dropwise to the heated benzyl ether at a rate of 220. mu.L/min with a syringe pump, stirred vigorously throughout the process to ensure thorough mixing of the liquids, and after completion of the addition, the reaction was allowed to continue to heat at 250 ℃ for 2 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, the product was dissolved in 1.5mL of methylene chloride, precipitated by dropping into 40mL of methanol, and the solution was filtered off by suction, and purified by repeating precipitation three times. After drying in a vacuum drying oven, the product was obtained as a white powder: single-stranded nanoparticles (SCNP P (S-r-bcbS) -OH)230mg, yield 92%.
Step 2: 600mg (0.094mmol) of SCNP P (S-r-bcbS) -OH obtained in step 1 was dissolved in 10mL of anhydrous dichloromethane in a single-neck round-bottom flask, 30.5mg (0.386mmol) of pyridine was added, stirring was performed at 0 ℃ in an ice bath, after the solvent was completely cooled, 118. mu.L (215.9mg, 0.939mmol) of 2-bromoisobutyryl bromide was added dropwise at a rate of 35. mu.L/min, and after the addition was completed, the reaction was stirred at room temperature for 24 hours. After the reaction is finished, transferring the solvent into a separating funnel, adding 40mL of dichloromethane for dilution, repeatedly extracting with 100mL of deionized water for three times to remove unreacted small molecular substances, after the extraction is finished, adding anhydrous sodium sulfate into the solution for dewatering, performing suction filtration to remove the anhydrous sodium sulfate, performing rotary evaporator to spin dry the solvent, fully dissolving the product with 2mL of dichloromethane, dropwise adding the product into 60mL of methanol for precipitation, finally performing suction filtration to remove liquid, and drying in a vacuum drying oven to obtain a white powdery product: single-stranded nanoparticles containing a group of acyl bromide (SCNP P (S-r-bcbS) -Br)570mg, yield 95%.
SCNP P (S-r-bcbS) -Br was dissolved in 10mL of N, N-Dimethylformamide (DMF) in a single-necked round-bottomed flask, and 30.4mg (0.468mmol) of sodium azide was added. The reaction is stirred at normal temperature for 24 hours. After the reaction is finished, 150mL of deionized water is directly added into the solution for washing, the product can be separated out as an insoluble substance, meanwhile, redundant sodium azide is washed away, the washing is repeated for three times, the liquid is removed by suction filtration, and the white powdery product is obtained after the drying in a vacuum drying oven: single-chain nanoparticles with azido groups (SCNP P (S-r-bcbS) -N3)547mg, yield 96%.
And step 3: 400mg (0.0625mmol) of the SCNP P (S-r-bcbS) -N from step 23Dissolving the mixture in 5mL of toluene in a 50mL Schlenk solvent storage bottle, adding 81.6mg (0.103mmol) of VPOSS-alkyne and 26.2mg (0.117mmol) of cuprous bromide, carrying out refrigeration and air-extraction on a reaction device on a vacuum double-row pipe three times, discharging oxygen in a system, opening the Schlenk bottle under the condition of continuously introducing nitrogen, quickly adding 32.4mg (0.187mmol) of PMDETA, vacuumizing the system after sealing, finally unfreezing the solution, and stirring at normal temperature for reaction for 12 hours. After completion of the reaction the solution was transferred directly into a silica gel column and washed with the eluent dichloromethane: the petroleum ether (2:1) mixed solvent is firstly used for flushing unreacted raw materials with the minimum polarity, and then the eluent dichloromethane is used for: the product was collected by filtration with a mixture of solvents of methanol (9:1), the solvent was dried by spinning, the product was dissolved in 2mL of dichloromethane and then precipitated in 60mL of methanol, and the liquid was removed by suction filtration. After drying in a vacuum drying oven, the product was obtained as a white powder: polyhedral oligomeric silsesquioxane (SCNP VPOSS-P (S-r-bcbS)) with single-chain nanoparticles as tails 252mg with a yield of 63%.
And 4, step 4: 100mg (0.0135mmol) of VPOSS-P (S-r-bcbS) obtained in step 3 was dissolved in 1mL of tetrahydrofuran in a 20mL transparent glass bottle, 71.5mg (0.777mmol) of 2-mercaptoacetic acid was added thereto and mixed with stirring, 2mg (0.0149mmol) of 2, 2-dimethoxy-2-phenylacetophenone (DMPA) was added thereto, and the mixture was irradiated with ultraviolet light at 365nm for 10min with stirring. After the reaction is finished, directly dropwise adding the solution into 30mL of methanol for precipitation, centrifuging the precipitated turbid solution on a centrifuge at the speed of 10000r/min, pouring out the supernatant after the centrifugation is finished, dissolving the precipitate with 2mL of tetrahydrofuran, precipitating in the methanol, centrifuging again, and repeatedly purifying for three times to obtain the final product: the tail chain is 79mg of the giant surfactant with single-chain nano particles (SCNP APOSS-P (S-r-bcbS)), and the yield is 79%.
The giant surfactant provided by the invention can be applied to the fields of energy, catalysis or biomedical engineering, and has wide application prospect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (9)

1. A giant surfactant has a structural formula shown as a formula (I):
Figure FDA0003079421100000011
in the formula (I), R1Denotes linear poly (styrene-R-benzocyclobutene) intramolecular cross-linking, R2Is selected from C2～C6A straight or branched alkyl alcohol of (C)2～C6Linear or branched polyol, benzyl alcohol, C2～C6One or more of linear or branched carboxylic acids of (a); m is the number of styrene monomers in a single molecule, n is the number of benzocyclobutene monomers in a single molecule, m: n is (2-9): 1.
2. a method for preparing the giant surfactant of claim 1, which comprises the steps of: the method comprises the following steps:
1) performing intramolecular crosslinking initiated by cycloaddition reaction of benzocyclobutene on linear poly (styrene-r-benzocyclobutene) containing hydroxyl to prepare single-chain nanoparticles containing hydroxyl;
2) preparing single-chain nanoparticles containing acyl halide groups by nucleophilic substitution reaction of the hydroxyl-containing single-chain nanoparticles and acyl halide, and then preparing single-chain nanoparticles containing azide groups by azide reaction;
3) carrying out azide-alkyne click chemical reaction on single-chain nanoparticles containing azide groups and mono-alkynyl heptavinyl polyhedral oligomeric silsesquioxane to prepare the polyhedral oligomeric silsesquioxane containing the single-chain nanoparticles;
4) the polyhedral oligomeric silsesquioxane containing single-chain nanoparticles is subjected to sulfydryl-double bond click chemical reaction to prepare the giant surfactant with the tail chain being the single-chain nanoparticles.
3. The method of claim 2, wherein the surfactant is prepared by: in the step 1), the cycloaddition reaction specifically comprises: and (2) dropwise adding the hydroxyl-containing linear poly (styrene-r-benzocyclobutene) solution into an organic solvent, and heating for reaction to obtain the hydroxyl-containing single-chain nano particle.
4. The method of claim 3, wherein the surfactant is selected from the group consisting of: in the step 1), the structural formula of the hydroxyl-containing linear poly (styrene-r-benzocyclobutene) is shown as a formula (II):
Figure FDA0003079421100000012
in formula (ii), m is the number of styrene monomers in a single molecule, n is the number of benzocyclobutene monomers in a single molecule, m: n is (2-9): 1;
the structural formula of the hydroxyl-containing single-chain nano particle is shown as the formula (III):
Figure FDA0003079421100000021
in formula (iii), m is the number of styrene monomers in a single molecule, n is the number of benzocyclobutene monomers in a single molecule, m: n is (2-9): 1; r1Represents linear poly (styrene-r-benzocyclobutene) intramolecular crosslinks containing hydroxyl groups.
5. The method of claim 2, wherein the surfactant is prepared by: in the step 2), the nucleophilic substitution reaction specifically comprises: dissolving the hydroxyl-containing single-chain nano-particles in an organic solvent, adding an alkaline catalyst, and then adding acyl halide to react to obtain the acyl halide-group-containing single-chain nano-particles.
6. The method of claim 5, wherein the surfactant is selected from the group consisting of: in the step 2), the azide reaction is specifically as follows: dissolving the single-chain nano-particles containing acyl halide groups in an organic solvent, adding an azide reagent, and reacting to obtain the single-chain nano-particles containing the azide groups.
7. The method of claim 2, wherein the surfactant is prepared by: in the step 3), the azide-alkyne click chemical reaction specifically comprises the following steps: dissolving single-chain nanoparticles containing azide groups in an organic solvent, adding monoalkynyl heptavinyl polyhedral oligomeric silsesquioxane, cuprous salt and a ligand to react to obtain the polyhedral oligomeric silsesquioxane containing the single-chain nanoparticles; the structural formula of the monoalkynyl heptavinyl polyhedral oligomeric silsesquioxane is shown as a formula (IV):
Figure FDA0003079421100000022
8. the method of claim 2, wherein the surfactant is prepared by: in the step 4), the mercapto-double bond click chemistry reaction specifically comprises: the polyhedral oligomeric silsesquioxane containing single-chain nanoparticles is dissolved in an organic solvent, a thiol compound containing hydroxyl and a photoinitiator are added, and the reaction is carried out under the illumination to obtain the giant surfactant with the tail chain being the single-chain nanoparticles.
9. The use of the giant surfactant of claim 1 in the fields of energy, catalysis, or biomedical engineering.
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