CN112812302A - Novel water-soluble polymerizable POSS and preparation method thereof - Google Patents
Novel water-soluble polymerizable POSS and preparation method thereof Download PDFInfo
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Abstract
The invention provides novel water-soluble polymerizable POSS and a preparation method thereof, and the preparation method comprises the following steps: (1) dissolving cage type oligomeric silsesquioxane and 3-mercapto-1-propane sodium sulfonate in a solvent, adding an auxiliary agent, and reacting under the protection of inert gas; (2) and (2) performing rotary evaporation or filtration on the solution obtained after the reaction in the step (1) to obtain solid powder, washing, dissolving in deionized water, centrifuging to obtain a supernatant, and performing freeze drying to obtain white solid powder. The novel water-soluble and polymerizable POSS is prepared, and the novel POSS molecule simultaneously has sodium sulfonate group and carbon-carbon double bond, so that on one hand, the POSS has good water solubility, and the solubility in water is 1300 mg/ml; on the other hand, the compound can be used as a monomer or a crosslinking agent for radical polymerization, and can also be subjected to mercapto-ene reaction.
Description
Technical Field
The invention belongs to the technical field of organic silicon materials, and particularly relates to novel water-soluble polymerizable POSS and a preparation method thereof.
Background
Polyhedral oligomeric silsesquioxane (POSS) is an organic-inorganic hybrid material at the molecular level. The inner core of POSS is a regular inorganic cage structure composed of Si-O-Si, and the peripheral vertexes are a plurality of different or same organic substituent groups. The special molecular structure of POSS endows the POSS with the characteristics of synergistic advantages of organic and inorganic components, such as good thermal stability, excellent thermo-mechanical property and good interfacial compatibility with polymers, and is an excellent nano filler for modifying polymers.
The POSS molecule with the size of 1-3 nm is introduced into the polymer, so that the composite material has good thermal stability, high mechanical strength, high temperature resistance, oxidation resistance and aging resistance, has the performances of light, dielectric, flame retardance and the like, and is applied to the fields of flame retardance, super-hydrophobicity, coatings, high-performance materials and the like. POSS is widely applied in the field of traditional polymer modification, and in recent years, due to the characteristics of good biocompatibility, good stability, no toxicity and the like, the POSS also attracts the attention of researchers in the field of biomedical materials, is called a new-generation biomedical material, and is reported in documents as a gene transfer vector, a heart scaffold material and a tissue engineering material.
Compared with the widely reported POSS-based polymer materials, the preparation and synthesis research of POSS molecules are relatively few. At present, the commercialized POSS with reaction functional groups has few types, mostly has single functional groups or POSS with the same functional groups, is expensive, and most of the POSS is insoluble in water and cannot be used under physiological conditions. The literature also reports the synthesis methods of some asymmetric bifunctional POSS, but the subsequent separation and purification are more complicated, so that the popularization and the application of the bifunctional POSS are limited. The simple and efficient preparation method of POSS with water-soluble polymerizable functional groups has become a technical problem to be solved urgently.
Disclosure of Invention
The invention provides novel water-soluble and polymerizable POSS and a preparation method thereof, and solves the problems that the POSS is insoluble in water, cannot be used under physiological conditions and is complex in preparation method at present.
The technical scheme for realizing the invention is as follows:
a preparation method of novel water-soluble polymerizable POSS comprises the following steps:
(1) dissolving cage type oligomeric silsesquioxane and 3-mercapto-1-propane sodium sulfonate in a solvent, adding an auxiliary agent, and reacting under the protection of inert gas;
(2) and (2) performing rotary evaporation or filtration on the solution obtained after the reaction in the step (1) to obtain solid powder, washing, dissolving in deionized water, centrifuging to obtain a supernatant, and performing freeze drying to obtain white solid powder.
Preferably, the above method is divided into the following two cases:
in the first case:
in the step (1), the cage type oligomeric silsesquioxane is acryloxy POSS or methacryloxy POSS, the acryloxy POSS or methacryloxy POSS and 3-mercapto-1-propane sodium sulfonate (MPSA) are weighed according to a certain molar ratio and dissolved in methanol, mercapto-ene Michael reaction of a nucleophilic mechanism is carried out under the action of triethylamine or n-butylamine, the reaction is carried out at normal temperature under the protection of inert gas for 6-8h by stirring, the obtained solution is subjected to rotary evaporation after the reaction to obtain white solid particles, the solid particles are dissolved in water for centrifugation to obtain clear liquid, and the white solid particles are obtained by freeze drying to prepare the novel water-soluble polymerizable POSS.
When the cage type oligomeric silsesquioxane is acryloxy POSS or methacryloxy POSS, the auxiliary agent is triethylamine or n-butylamine.
In the second case:
the cage type oligomeric silsesquioxane in the step (1) is octavinyl POSS or octavinyl disilyl POSS; weighing octavinyl POSS or octavinyl disilyl POSS and 3-mercapto-1-propane sodium sulfonate according to a certain molar ratio, dissolving the octavinyl POSS or octavinyl disilyl POSS in a toluene solvent, dissolving the 3-mercapto-1-propane sodium sulfonate in a methanol solvent, uniformly mixing the two solutions, initiating a mercapto-alkene addition reaction for 1-2h under an ultraviolet light condition through a photoinitiator to generate a free radical mechanism, carrying out suction filtration and washing on the obtained solution after the reaction to obtain white solid particles, dissolving the solid particles in water, centrifuging to obtain clear liquid, and carrying out freeze drying to obtain the white solid particles, thereby preparing the novel water-soluble polymerizable POSS.
When the cage type oligomeric silsesquioxane is an octavinyl POSS or octavinyldisilyl POSS, the auxiliary agent is one of benzoin dimethyl ether (DMPA), 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone (Irgacure 2959), 1-hydroxycyclohexyl phenyl ketone (Irgacure 184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (Darocur 1173), phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (Irgacure 819), 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone (Irgacure 907) and 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone (Irgacure 369); the solvent is a mixed solvent of toluene or methanol.
In the above step, the molar ratio of POSS to 3-mercapto-1-propane sodium sulfonate is 1: (2-7):
the water-soluble polymerizable POSS prepared by the preparation method has the following structural formula:
the water-soluble polymerizable POSS simultaneously has sodium sulfonate group and carbon-carbon double bond, and the solubility in water is 240-1300 mg/mL.
The water-soluble polymerizable POSS is used as a monomer or a crosslinking agent for free radical polymerization, and can also be subjected to sulfydryl-alkene reaction.
The water-soluble polymerizable POSS is used for preparing a hydrogel material in aqueous solution through high-molecular polymerization or Michael addition, and is used in the fields of flexible wearable devices, super capacitors, lithium ion battery electrodes and electrolyte materials.
The invention has the beneficial effects that:
(1) the novel water-soluble and polymerizable POSS is prepared, and the novel POSS molecule simultaneously has sodium sulfonate group and carbon-carbon double bond, so that on one hand, the POSS has good water solubility, and the solubility in water is 1300 mg/ml; on the other hand, the compound can be used as a monomer or a crosslinking agent for radical polymerization, and can also be subjected to mercapto-ene reaction.
(2) The invention provides a method for preparing water-soluble and polymerizable POSS, which has the advantages of mild reaction conditions, short time, simple operation, high yield and simple and convenient post-treatment.
(3) The water-soluble polymerizable POSS prepared by the invention can be used as a comonomer or a crosslinking agent to be polymerized with a macromolecule in an aqueous solution or be subjected to Michael addition to prepare a hydrogel material with high mechanical property and high conductivity, and can be used in the fields of flexible wearable devices, super capacitors, lithium ion battery electrodes, electrolyte materials and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a fourier infrared spectrum (FTIR) of a novel water-soluble and polymerizable acryloxy poss (saps) provided in example 1 of the present invention.
FIG. 2 shows the NMR spectrum of a novel water-soluble polymerizable acryloxy POSS (SAPS) in example 1 of the present invention (see1H-NMR）。
FIG. 3 is a NMR spectrum of a novel water-soluble and polymerizable acryloxy POSS (SAPS) provided in example 1 of the present invention: (13C-NMR）。
FIG. 4 shows a nuclear magnetic resonance silicon spectrum of a novel water-soluble polymerizable acryloxy POSS (SAPS) provided in example 1 of the present invention29Si-NMR）。
Figure 5 is an X-ray diffraction pattern (XRD) of the novel water-soluble and polymerizable acryloxy poss (saps) provided in example 1 of the present invention.
Fig. 6 is a thermogravimetric plot (TG) of the novel water-soluble and polymerizable acryloxy poss (saps) provided in example 1 of the present invention.
Fig. 7 is a Scanning Electron Micrograph (SEM) of the novel water-soluble and polymerizable acryloxy poss (saps) provided in example 1 of the present invention.
FIG. 8 is a Fourier Infrared Spectroscopy (FTIR) of novel water-soluble and polymerizable vinyl POSS (MP-POSS) provided in example 2 of the present invention.
FIG. 9 is a NMR spectrum of a novel water-soluble and polymerizable vinyl POSS (MP-POSS) provided in example 2 of the present invention (1H-NMR）。
FIG. 10 is a nuclear magnetic resonance carbon spectrum of a novel water-soluble and polymerizable vinyl POSS (MP-POSS) provided in example 2 of the present invention (13C-NMR）。
FIG. 11 is a NMR spectrum of novel water-soluble and polymerizable vinyl POSS (MP-POSS) provided in example 2 of the present invention (29Si-NMR）。
FIG. 12 is an X-ray diffraction pattern (XRD) of the novel water-soluble and polymerizable vinyl POSS (MP-POSS) provided in example 2 of this invention.
FIG. 13 is a thermogravimetric plot (TG) of novel water-soluble and polymerizable vinyl POSS (MP-POSS) provided in example 2 of the present invention.
FIG. 14 is a Scanning Electron Micrograph (SEM) of novel water soluble and polymerizable vinyl POSS (MP-POSS) provided in example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation steps are as follows:
the method comprises the following steps: weighing acryloxy POSS and 3-mercapto-1-propane sodium sulfonate according to a molar ratio of 1:4, accurately weighing 1.3218 g (0.001 mol, 1321.75 g/mol) acryloxy POSS and 0.7128 g (0.004 mol, 178.21 g/mol) 3-mercapto-1-propane sodium sulfonate, dissolving the two reactants in 100 ml of methanol solution, adding 0.1 g triethylamine, protecting by inert gas, and stirring at normal temperature for reaction for 6 hours;
step two: and (3) rotationally evaporating the solution obtained after the reaction in the step one to obtain white solid particles, dissolving the solid particles in water, centrifuging to obtain clear liquid, and freeze-drying to obtain the white solid particles, so that the novel water-soluble polymerizable acryloxy POSS (SAPS) is obtained, and the yield is about 95%.
Example 2
The preparation steps are as follows:
the method comprises the following steps: octavinyl POSS and 3-mercapto-1-propane sodium sulfonate are weighed according to the molar ratio of 1:4, 0.633 g (0.001 mol, 633.04 g/mol) of octavinyl POSS is accurately weighed and dissolved in 50 ml of toluene solution, and 0.7128 g (0.004 mol, 178.21 g/mol) of 3-mercapto-1-propane sodium sulfonate is dissolved in 50 ml of methanol solution;
step two: uniformly mixing the toluene solution and the methanol solution obtained in the step one in a single-neck flask, adding 0.05 g of 2, 2-dimethoxy-2-phenylacetophenone (DMPA) serving as a photoinitiator under the protection of inert gas, and stirring for reaction for 2 hours under the condition of ultraviolet light;
step three: and (3) filtering the reaction liquid obtained in the third step to obtain solid particles, washing the solid particles by using ethanol, dissolving the solid particles in water, centrifuging to obtain clear liquid, and freeze-drying to obtain white solid particles, namely the novel water-soluble polymerizable vinyl POSS (MP-POSS), wherein the yield is about 90%.
Example 3
The preparation steps are as follows:
the method comprises the following steps: weighing acryloxy POSS and 3-mercapto-1-propane sodium sulfonate according to a molar ratio of 1:2, accurately weighing 1.3218 g (0.001 mol, 1321.75 g/mol) acryloxy POSS and 0.3564 g (0.002 mol, 178.21 g/mol) 3-mercapto-1-propane sodium sulfonate, dissolving the two reactants in 100 ml of methanol solution, adding 0.08 g n-butylamine, protecting by inert gas, and stirring at normal temperature for reaction for 6 hours;
step two: and (3) rotationally evaporating the solution obtained after the reaction in the step one to obtain white solid particles, dissolving the solid particles in water, centrifuging to obtain clear liquid, and freeze-drying to obtain the white solid particles, so that the novel water-soluble polymerizable acryloxy POSS (SAPS) is obtained, and the yield is about 91%.
Example 4
The preparation steps are as follows:
the method comprises the following steps: weighing acryloxy POSS and 3-mercapto-1-propane sodium sulfonate according to a molar ratio of 1:7, accurately weighing 1.3218 g (0.001 mol, 1321.75 g/mol) acryloxy POSS and 1.2474 g (0.007 mol, 178.21 g/mol) 3-mercapto-1-propane sodium sulfonate, dissolving the two reactants in 200 ml methanol solution, adding 0.2 g triethylamine, protecting with inert gas, and stirring at normal temperature for reaction for 6 hours;
step two: and (3) rotationally evaporating the solution obtained after the reaction in the step one to obtain white solid particles, dissolving the solid particles in water, centrifuging to obtain clear liquid, and freeze-drying to obtain the white solid particles, so that the novel water-soluble polymerizable acryloxy POSS (SAPS) is obtained, and the yield is about 93%.
Example 5
The preparation steps are as follows:
the method comprises the following steps: octavinyl POSS and 3-mercapto-1-propane sodium sulfonate are weighed according to the molar ratio of 1:2, 0.633 g (0.001 mol, 633.04 g/mol) of octavinyl POSS is accurately weighed and dissolved in 50 ml of toluene solution, 0.3564 g (0.002 mol, 178.21 g/mol) of 3-mercapto-1-propane sodium sulfonate is dissolved in 50 ml of methanol solution;
step two: uniformly mixing the toluene solution and the methanol solution obtained in the step one in a single-neck flask, adding 0.05 g of photoinitiator 1-hydroxycyclohexyl phenyl ketone (HCPK) under the protection of inert gas, and stirring and reacting for 1 h under the condition of ultraviolet light;
step three: and (3) filtering the reaction liquid obtained in the third step to obtain solid particles, washing the solid particles by using ethanol, dissolving the solid particles in water, centrifuging to obtain clear liquid, and freeze-drying to obtain white solid particles, namely the novel water-soluble polymerizable vinyl POSS (MP-POSS), wherein the yield is about 92%.
Example 6
The preparation steps are as follows:
the method comprises the following steps: weighing octavinyl POSS and 3-mercapto-1-propane sodium sulfonate according to a molar ratio of 1:7, accurately weighing 1.266 g (0.002 mol, 633.04 g/mol) of octavinyl POSS, dissolving the octavinyl POSS in 150 ml of toluene solution, and accurately weighing 2.4948 g (0.014 mol, 178.21 g/mol) of 3-mercapto-1-propane sodium sulfonate, dissolving the octavinyl POSS in 150 ml of methanol solution;
step two: uniformly mixing the toluene solution and the methanol solution obtained in the step one in a single-neck flask, adding 0.15 g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (HMPP), protecting with inert gas, and stirring under the condition of ultraviolet light for reaction for 2 hours;
step three: and (3) filtering the reaction liquid obtained in the third step to obtain solid particles, washing the solid particles by using ethanol, dissolving the solid particles in water, centrifuging to obtain clear liquid, and freeze-drying to obtain white solid particles, namely the novel water-soluble polymerizable vinyl POSS (MP-POSS), wherein the yield is about 94%.
Fig. 1 is a fourier infrared spectrum (FTIR) of a novel water-soluble and polymerizable acryloxy poss (saps) provided in example 1 of the present invention. The main basis for preliminarily judging whether the mercapto-alkene Michael addition of the mercapto sodium sulfonate and the acryloxy POSS occurs is as follows: whether the infrared spectrogram of SAPS has a characteristic absorption peak of sulfydryl and a characteristic absorption peak of sulfonic acid group. As shown by the curve in FIG. 1, the stretching vibration peak of the thiol group on MPSA appeared at 2556 cm-1However, no stretching vibration peak of the thiol group was observed in SAPS, and it was presumed that the thiol group may be oxidized or added to the double bond of the acryloyloxy group. In addition 1052 cm on the SAPS infrared spectrum-1Asymmetric and symmetric stretching vibration peaks of sulfonic acid groups are found, and the Michael addition reaction of the mercapto sodium sulfonate and the acryloxy POSS can be comprehensively estimated, which is consistent with the experimental result that the obtained sulfonic POSS is very soluble in water. At the same time, the length is 1112 cm-1A stretching vibration absorption peak of Si-O-Si was also found, indicating that the cage structure of POSS was not destroyed. In addition, at 1636 cm-1An infrared characteristic absorption peak of the carbon-carbon double bond is found, which can ensure that SAPS is used as a cross-linking agent and propyleneThe acrylic acid and acrylamide monomers form a hydrogel.
FIG. 2 shows the NMR spectrum of a novel water-soluble polymerizable acryloxy POSS (SAPS) in example 1 of the present invention (see1H-NMR). As can be seen from the figure, δ =0.77 ppm (a) is an absorption peak of a hydrogen atom on a methylene group directly bonded to Si. δ =2.05 ppm (i) is the absorption peak of the hydrogen atom on the methylene group at the β position linked to the sodium sulfonate group. Since in SAPS1In the H-NMR chart, the area of the atomic absorption peak under different chemical environments is proportional to the number of atoms, so the area can be 1 by integrating the areas based on a. The area of i was found to be 0.48, approximately 0.5 times the area of a, indicating a 4:1 molar ratio of reaction of MPSA molecules with acryloxy POSS.
FIG. 3 is a NMR spectrum of a novel water-soluble and polymerizable acryloxy POSS (SAPS) provided in example 1 of the present invention: (13C-NMR). As can be seen from the figure, an absorption peak at δ =49.82 ppm appears for the carbon atom at α position of the sodium sulfonate group; 34.43 ppm (g), 26.15 ppm (h) of-CH associated with C = O2-CH2Characteristic peaks for two carbons. This indicates that MPSA undergoes an addition reaction with acryloxy POSS. Nuclear magnetic resonance carbon spectrum by SAPS: (13C NMR), it can be seen that each carbon atom marked with a letter on the SAPS structure corresponds one-to-one to each characteristic peak position marked with a letter.
FIG. 4 shows a nuclear magnetic resonance silicon spectrum of a novel water-soluble polymerizable acryloxy POSS (SAPS) provided in example 1 of the present invention29Si-NMR). As can be seen from the figure, the sharp peak appears at one position to indicate that the chemical environment of 8 silicon atoms in the product is the same, the SAPS only contains one form of silicon atoms, which indicates that the product has a highly symmetrical structure, and other miscellaneous peaks do not appear in the silicon spectrum, which indicates that the product has a uniform structure and better purity.
Figure 5 is an X-ray diffraction pattern (XRD) of the novel water-soluble and polymerizable acryloxy poss (saps) provided in example 1 of the present invention.
Fig. 6 is a thermogravimetric plot (TG) of the novel water-soluble and polymerizable acryloxy poss (saps) provided in example 1 of the present invention.
Fig. 7 is a Scanning Electron Micrograph (SEM) of the novel water-soluble and polymerizable acryloxy poss (saps) provided in example 1 of the present invention.
FIG. 8 is a Fourier Infrared Spectroscopy (FTIR) of novel water-soluble and polymerizable vinyl POSS (MP-POSS) provided in example 2 of the present invention. As can be seen from the figure, the main characteristic peaks of the Fourier transform infrared spectrogram of the MP-POSS are as follows: at 1181 cm-1、1052 cm-1Is the stretching vibration peak of S = O in the sulfonic acid group; 746 cm-1Is- (CH)2)3-a deformation vibration peak of C-H in (a); 1100 cm-1Is a characteristic peak of Si-O-Si, which indicates that a large amount of Si-O-Si structures exist in the product molecules. These fourier transform infrared spectroscopy data indicate that octavinyl POSS has successfully click reacted with MPSA. And exists at 1640 cm-1C = C stretching vibration peak; 2972 cm-1、2940 cm-1、2880 cm-1C-H stretching vibration peak of (a); 1448 cm-1、1410 cm-1And 1350 cm−1The presence of C-H deformation vibration peaks of (a) confirms the presence of Si-CH = CH. The structure of the target product MP-POSS can be preliminarily determined to be basically consistent with the designed structure through the analysis.
FIG. 9 is a NMR spectrum of a novel water-soluble and polymerizable vinyl POSS (MP-POSS) provided in example 2 of the present invention (1H-NMR). As can be seen from the figure: the chemical shift distribution of hydrogen atoms in the MP-POSS molecule is in the range of 1.17 ppm to 6.25 ppm. Wherein 1.17 ppm (a) is Si-CH22.74 ppm (c) is CH2-S-CH2CH in (1)2Above hydrogen atom characteristic peak, 2.06 ppm (b) is CH2-CH2-CH2In the middle position CH2Upper hydrogen atom characteristic peak, 3.04 ppm (d) is CH2-SO3Characteristic peak of hydrogen atom on Na, characteristic peak of hydrogen atom on Si-CH at 6.08 ppm (e), characteristic peak of hydrogen atom on Si-CH at 6.25 ppm (f)2And CH in (1) to which CH is bonded2Upper hydrogen atom characteristic peak, 4.79 ppm is D2Solvent peak for O. No obvious impurity peak appears in the figure, which shows that the polymer has uniform structure and better purity.
FIG. 10 is a nuclear magnetic resonance carbon spectrum of a novel water-soluble and polymerizable vinyl POSS (MP-POSS) provided in example 2 of the present invention (13C-NMR). As can be seen from the figure: 128.35 ppm (g), 139.04 ppm (f) correspond to CH on POSS2Characteristic peaks for two carbons in CH; 12.20 ppm (a) of Si-CH2Characteristic peak of carbon atom; 23.58 ppm of (b) is-CH2-a characteristic peak of carbon atoms in S; 29.95 ppm (c) is S-CH2-a characteristic peak of carbon atoms; 26.46 ppm (d) is CH2-CH2-CH2Characteristic peak of the middle carbon atom in (1); 50.83 ppm (e) is CH2-SO3Characteristic peak of carbon atom in Na.
Nuclear magnetic resonance hydrogen spectrum from MP-POSS (1H-NMR) and nuclear magnetic resonance carbon Spectroscopy (C13C-NMR), it can be seen that each hydrogen atom and carbon atom of the MP-POSS structure marked with letters corresponds one-to-one to the position of each characteristic peak marked with letters.
FIG. 11 is a NMR spectrum of novel water-soluble and polymerizable vinyl POSS (MP-POSS) provided in example 2 of the present invention (29Si-NMR). As can be seen from the figure: the MP-POSS product structure contains two types of Si atoms with different chemical environments, and the chemical shifts are-68.12 ppm and-79.95 ppm respectively. 79.95 ppm (b) of Si-CH = CH2Characteristic peak of middle silicon atom; 68.12 ppm of Si-CH at (a)2Characteristic peak of middle silicon atom. No other miscellaneous peak appears in the silicon spectrum, which indicates that the MP-POSS product has uniform structure and better purity, and other byproducts are excluded.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of novel water-soluble polymerizable POSS is characterized by comprising the following steps:
(1) dissolving cage type oligomeric silsesquioxane and 3-mercapto-1-propane sodium sulfonate in a solvent, adding an auxiliary agent, and reacting under the protection of inert gas;
(2) and (2) performing rotary evaporation or filtration on the solution obtained after the reaction in the step (1) to obtain solid powder, washing, dissolving in deionized water, centrifuging to obtain a supernatant, and performing freeze drying to obtain white solid powder.
2. The method for producing novel water-soluble polymerizable POSS as claimed in claim 1 wherein: the cage type oligomeric silsesquioxane in the step (1) is acryloxy POSS or methacryloxy POSS, and the solvent is methanol; the auxiliary agent is triethylamine or n-butylamine.
3. The method for producing novel water-soluble polymerizable POSS as claimed in claim 2, wherein: and (2) stirring and reacting for 6-8h at normal temperature under the protection of inert gas in the step (1).
4. The method for producing novel water-soluble polymerizable POSS as claimed in claim 1 wherein: the cage type oligomeric silsesquioxane in the step (1) is octavinyl POSS or octavinyl disilyl POSS; the auxiliary agent is one of benzoin dimethyl ether, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone or 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone; the solvent is a mixed solvent of toluene or methanol.
5. The method for producing novel water-soluble polymerizable POSS as claimed in claim 4 wherein: and (2) reacting for 1-2h under the protection of ultraviolet illumination and inert gas at normal temperature in the step (1).
6. The method for producing novel water-soluble polymerizable POSS as claimed in any one of claims 1 to 5, characterized in that: the mol ratio of POSS to 3-mercapto-1-propane sodium sulfonate in the step (1) is 1: (2-7).
7. The method of claim 6 producing a water-soluble polymerizable POSS having the formula:
8. the water-soluble polymerizable POSS of claim 7 wherein: the water-soluble polymerizable POSS simultaneously has sodium sulfonate group and carbon-carbon double bond, and the solubility in water is 240-1300 mg/mL.
9. The water-soluble polymerizable POSS of claim 7 or 8 wherein: the water-soluble polymerizable POSS is used as a monomer or a crosslinking agent for free radical polymerization, and can also be subjected to sulfydryl-alkene reaction.
10. The water-soluble polymerizable POSS of claim 9 wherein: the water-soluble polymerizable POSS is used for preparing a hydrogel material in aqueous solution through high-molecular polymerization or Michael addition, and is used in the fields of flexible wearable devices, super capacitors, lithium ion battery electrodes and electrolyte materials.
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