A method for detecting the content of alkylvinyl-containing cage octasilsesquioxane

Abstract

This invention provides a method for detecting the content of cage-like octameric silsesquioxanes containing alkyl vinyl groups, belonging to the field of organosilicon compound analysis and testing technology. The invention involves mixing the sample to be tested with a thiol compound and performing a click reaction to obtain a derivatized product; mixing the derivatized product with a solvent to obtain a test solution; performing high-performance liquid chromatography (HPLC) on the test solution to obtain the chromatographic peak area; and calculating the content of the cage-like octameric silsesquioxane containing alkyl vinyl groups based on the chromatographic peak area. This invention employs a thiol-ene click reaction to derivatize alkyl-substituted vinyl POSS, transforming isolated vinyl groups with weak UV absorption into thioether-bridged alkoxysilane functional groups with strong UV absorption. This solves the problem of weak UV absorption and low response values ​​in direct HPLC determination of alkyl-substituted vinyl POSS, significantly improving the detection sensitivity.

Description

Technical Field

[0001] This invention relates to the field of organosilicon compound analysis and testing technology, and in particular to a method for detecting the content of cage-like octameric silsesquioxanes containing alkyl vinyl groups. Background Technology

[0002] Alkyl-substituted vinyl octameric silsesquioxanes (POSS) are silsesquioxane compounds with a cage-like structure. Their molecular structure contains isolated vinyl functional groups and alkane functional groups, exhibiting good reactivity. They can be further derivatized through polymerization, addition, and other reactions, and are widely used in polymer modification, composite material preparation, and catalyst support. The content of alkyl-substituted vinyl POSS directly affects its derivatization reaction efficiency, product performance, and application effects. Therefore, establishing an accurate, efficient, and easy-to-operate method for determining the content of alkyl-substituted vinyl POSS is of great significance for its production, quality control, and application.

[0003] Currently, quantitative detection methods for alkyl-substituted vinyl POSS are scarce. Because their molecular structure lacks near-UV absorbing groups, their UV absorption is weak, resulting in indistinct peak shapes and low response values ​​when directly measured by high-performance liquid chromatography (HPLC), making accurate quantification difficult. Alkyl-substituted vinyl POSS have large molecular weights and high boiling points, making them undetectable by gas chromatography, and no suitable chemical methods exist for their determination. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a method for detecting the content of cage-like octameric silsesquioxanes containing alkyl vinyl groups. This invention utilizes a mercapto-ene click reaction to derivatize alkyl-substituted vinyl POSS, combined with high-performance liquid chromatography (HPLC) to achieve quantitative analysis. This method has the advantages of simple operation, high testing efficiency, good accuracy, and wide applicability.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for detecting the content of cage-like octameric silsesquioxanes containing alkyl vinyl groups, comprising the following steps: The test sample is mixed with a thiol compound and subjected to a click reaction (thiol-ene click reaction, derivatization reaction) to obtain a derivative product; the test sample includes a cage-like octameric silsesquioxane containing alkyl vinyl groups. The derivative is mixed with a solvent to obtain the test solution; The test solution was subjected to high performance liquid chromatography to obtain the chromatographic peak area of ​​the test solution; The content of the alkyl vinyl cage-like octameric silsesquioxane containing alkyl vinyl groups is calculated based on the chromatographic peak area of ​​the test solution.

[0006] Preferably, the thiol compound includes 3-mercaptopropyltrimethoxysilane.

[0007] Preferably, the molar ratio of the alkyl vinyl cage-like octameric silsesquioxane to the mercapto compound is 1:17 to 1:20.

[0008] Preferably, the temperature of the click reaction is 50~80℃ and the time is 10~30min.

[0009] Preferably, the click reaction is carried out in an organic solvent, and the ratio of the alkyl vinyl cage-like octameric silsesquioxane to the organic solvent is 20-100 mg: 1 mL.

[0010] Preferably, the click reaction is carried out under initiator conditions, wherein the amount of initiator is 0.1% to 2.0% of the total mass of the cage-like octameric silsesquioxane containing alkyl vinyl groups and the mercapto compound.

[0011] Preferably, the initiator includes a photoinitiator and / or a thermal initiator.

[0012] Preferably, the photoinitiator comprises one or more of α-hydroxybenzophenone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide (TPO), and ethyl 2,4,6-trimethylbenzoyl phenylphosphonate (TPO-L).

[0013] Preferably, the conditions for high-performance liquid chromatography (HPLC) detection include: a C18 reversed-phase column; a mobile phase of a mixture of acetonitrile and tetrahydrofuran, wherein the volume ratio of acetonitrile to tetrahydrofuran in the mixture is 70:30 to 95:5; isocratic elution; a mobile phase flow rate of 0.8 to 1.2 mL / min; a test wavelength of 210 to 230 nm; a column temperature of 25 to 40 °C; and an injection volume of 5 to 20 μL.

[0014] Preferably, the C18 reversed-phase chromatographic column has a column length of 150~250mm, a column diameter of 4.6mm, and a packing particle size of 5μm.

[0015] This invention provides a method for detecting the content of alkyl vinyl cage-like octameric silsesquioxanes, comprising the following steps: mixing a sample to be tested with a thiol compound and performing a click reaction to obtain a derivative; the sample to be tested includes alkyl vinyl cage-like octameric silsesquioxanes; mixing the derivative with a solvent to obtain a test solution; performing high-performance liquid chromatography (HPLC) on the test solution to obtain the chromatographic peak area of ​​the test solution; and calculating the content of the alkyl vinyl cage-like octameric silsesquioxanes based on the chromatographic peak area of ​​the test solution.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention uses a mercapto-ene click reaction to derivatize alkyl-substituted vinyl POSS, transforming isolated vinyl groups with weak UV absorption into thioether-bridged alkoxysilane functional groups with strong UV absorption. This solves the problem of weak UV absorption and low response value in direct liquid chromatography determination of alkyl-substituted vinyl POSS, and significantly improves the determination sensitivity. 2. The derivatization reaction conditions are mild, the reaction efficiency is high, the selectivity is strong, and the byproducts are few. This ensures the complete derivatization of alkyl-substituted vinyl POSS, avoids interference from unreacted samples on the determination results, and the derivatized products have stable structures, which facilitates subsequent chromatographic separation and determination. 3. The high-performance liquid chromatography (HPLC) determination conditions use a C18 reversed-phase column, which can effectively separate derivatized products from impurities, with symmetrical peak shapes and good resolution, avoiding measurement deviations caused by impurity peak overlap and improving measurement accuracy. 4. The entire determination method is simple to operate, with a clear process, short reaction time, and high testing efficiency. It does not require complex sample pretreatment equipment, has low cost, and is suitable for quality control and finished product testing in the production process of alkyl-substituted vinyl POSS, and has wide applicability. Attached Figure Description

[0017] Figure 1 This is the high-performance liquid chromatogram of Example 1; Figure 2 This is the high-performance liquid chromatogram of Example 2; Figure 3 This is the high-performance liquid chromatogram of Example 3; Figure 4 This is the high-performance liquid chromatogram of Example 4; Figure 5 This is the high-performance liquid chromatogram of Example 5; Figure 6 This is the high performance liquid chromatogram of Comparative Example 1. Detailed Implementation

[0018] This invention provides a method for detecting the content of cage-like octameric silsesquioxanes containing alkyl vinyl groups, comprising the following steps: The test sample is mixed with a thiol compound and subjected to a click reaction (thiol-ene click reaction, derivatization reaction) to obtain a derivative product; the test sample includes a cage-like octameric silsesquioxane containing alkyl vinyl groups. The derivative is mixed with a solvent to obtain the test solution; The test solution was subjected to high performance liquid chromatography to obtain the chromatographic peak area of ​​the test solution; The content of the alkyl vinyl cage-like octameric silsesquioxane containing alkyl vinyl groups is calculated based on the chromatographic peak area of ​​the test solution.

[0019] Unless otherwise specified, all raw materials used in this invention are commercially available products in the field.

[0020] This invention addresses the issue that alkyl-substituted vinyl POSSes lack characteristic absorption peaks when directly measured by liquid chromatography and the most common ultraviolet (200-400 nm) detector. It involves reacting the analyte alkyl-substituted vinyl POSS with a thiol compound under the action of an initiator to undergo a thiol-alkene click reaction, generating a thioether-bridged alkoxy-functionalized POSS derivative with ultraviolet absorption; utilizing the n→σ transition of the SC bond... * Leap: λ max With a wavelength of 210~215nm and logε=3.1, high-performance liquid chromatography (HPLC) was used for separation and determination with a UV detector. This method enables accurate determination of alkyl-substituted vinyl POSS in the UV-free range (200~400nm) by HPLC, solving the problem of the lack of quantitative analysis methods for alkyl-substituted vinyl POSS. The derivatization reaction conditions are mild with few side reactions, and the determination method is simple to operate and provides accurate and reliable results. It is suitable for industrial quality control and analysis of alkyl-substituted vinyl POSS.

[0021] This invention involves mixing the test sample with a thiol compound and performing a click reaction (thiol-ene click reaction, derivatization reaction) to obtain a derivatized product. The test sample includes a cage-like octameric silsesquioxane containing alkyl vinyl groups, and the click reaction generates a thioether-bridged alkoxy cage-like octameric silsesquioxane derivatized product. The thiol-ene click reaction has advantages such as mild reaction conditions, high reaction efficiency, strong selectivity, and few byproducts. By performing a thiol-ene click reaction between the alkyl-substituted vinyl POSS and the thiol compound, a functional group with UV absorption that is easily detectable by chromatography can be introduced into its molecular structure, thereby improving its testing performance.

[0022] In this invention, the thiol compound preferably includes 3-mercaptopropyltrimethoxysilane, and the generated thioether-bridged alkoxy cage-like octameric silsesquioxane derivative is octa(3-(3-trimethoxysilylpropylthio)propyl)cage-like octameric silsesquioxane, which has strong ultraviolet absorption and good separation effect on a C18 reversed-phase chromatographic column, enabling accurate quantification.

[0023] In this invention, the molar ratio of the cage-like octameric silsesquioxane containing alkyl vinyls to the mercapto compound is preferably 1:17 to 1:20, specifically 1:17, 1:18, 1:19 or 1:20. This molar ratio ensures that the vinyls in the alkyl-substituted vinyl POSS molecule react completely, avoiding the influence of unreacted vinyl residues on the derivatization effect.

[0024] In this invention, the click reaction is preferably carried out under initiator conditions. The amount of initiator is preferably 0.1% to 2.0% of the total mass of the cage-like octameric silsesquioxane containing alkyl vinyl groups and the mercapto compound. Specifically, it can be 0.1%, 0.5%, 1.0%, 1.5%, or 2.0%. This range of amounts ensures that the initiation reaction proceeds fully while avoiding the formation of byproducts due to excessive initiator, which could affect the detection results.

[0025] In this invention, the initiator preferably includes a photoinitiator and / or a thermal initiator.

[0026] In this invention, the photoinitiator preferably includes one or more of α-hydroxybenzophenone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide (TPO), and ethyl 2,4,6-trimethylbenzoyl phenylphosphonate (TPO-L).

[0027] In this invention, the temperature of the click reaction is preferably 50~80℃, specifically 50, 60, 70 or 80℃, and the time is preferably 10~30min, specifically 10, 20 or 30min. This reaction condition is mild and can ensure reaction efficiency while avoiding sample decomposition or side reactions.

[0028] In this invention, the click reaction is preferably carried out in an organic solvent, which preferably includes one or more of dichloromethane, trichloromethane, N,N-dimethylformamide (DMF), and tetrahydrofuran. The organic solvent has good solubility for both alkyl-substituted vinyl POSS and mercapto compounds, which can ensure the uniformity of the reaction system and improve the reaction efficiency. The ratio of the cage-like octameric silsesquioxane containing alkyl vinyls to the organic solvent is preferably 20~100 mg:1 mL, specifically 20 mg:1 mL, 40 mg:1 mL, 60 mg:1 mL, 80 mg:1 mL, or 100 mg:1 mL. This concentration range can balance reaction efficiency and the accuracy of subsequent measurements.

[0029] After obtaining the derivative, the present invention mixes the derivative with a solvent to obtain the test solution.

[0030] In this invention, the solvent is preferably the same as the organic solvent described in the above scheme to avoid the precipitation of derivative products due to solvent differences and to ensure the stability of the sample solution to be tested.

[0031] In this invention, the volume of the system obtained after mixing is preferably 10~50mL, and can be flexibly adjusted according to the sample concentration to ensure that the test signal is within the optimal response range of the instrument.

[0032] After the mixing is completed, it is preferable to use a 0.22~0.45μm organic phase filter membrane for filtration to effectively remove insoluble impurities in the reaction solution and avoid impurities interfering with chromatographic determination. Then, the solution is diluted with the mobile phase to obtain the test solution.

[0033] After obtaining the test solution, the present invention performs high performance liquid chromatography on the test solution to obtain the chromatographic peak area of ​​the test solution.

[0034] In this invention, the preferred conditions for high-performance liquid chromatography (HPLC) detection include: using a C18 reversed-phase column, which has good separation effect on derivatized products; the mobile phase is a mixture of acetonitrile and tetrahydrofuran, wherein the volume ratio of acetonitrile to tetrahydrofuran in the mixture is 70:30 to 95:5, which can effectively separate derivatized products from impurities and avoid damage to the C18 reversed-phase column due to excessive tetrahydrofuran concentration; the elution method is isocratic elution; the mobile phase flow rate is 0.8 to 1.2 mL / min, specifically 1.0 mL / min, with a reasonable flow rate setting to avoid excessive separation time or peak diffusion; the test wavelength is 210 to 230 nm, specifically 213 nm, at which the derivatized products have strong ultraviolet absorption, improving test sensitivity; the column temperature is 25 to 40 °C, specifically 36 °C; and the injection volume is 5 to 20 μL, specifically 10 μL, to ensure symmetrical chromatographic peaks and stable separation effect.

[0035] In this invention, the C18 reversed-phase chromatographic column is preferably 150-250 mm in length, preferably 4.6 mm in diameter, and preferably 5 μm in particle size of packing material.

[0036] After obtaining the chromatographic peak area of ​​the test solution, the present invention calculates the content of the cage-like octameric silsesquioxane containing alkyl vinyl groups based on the chromatographic peak area of ​​the test solution.

[0037] The present invention preferably uses the peak area of ​​the derivative obtained by the same click reaction and high performance liquid chromatography test of the external standard as a reference to calculate the content of the cage-like octameric silsesquioxane containing alkyl vinyl groups; or calculates the content of the cage-like octameric silsesquioxane containing alkyl vinyl groups by normalization method.

[0038] In view of the lack of a suitable and accurate quantitative method for the determination of alkyl-substituted vinyl POSS in the existing technology, the present invention establishes an accurate method for the determination of alkyl-substituted vinyl POSS content. This method derivatizes alkyl-substituted vinyl POSS through a mercapto-ene click reaction and combines it with high performance liquid chromatography to achieve quantitative analysis. It has the advantages of simple operation, high testing efficiency, good accuracy and strong applicability.

[0039] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0040] The alkyl-substituted vinyl POSS used in the examples and comparative examples are all octavinyl POSS.

[0041] Example 1 A method for determining the purity of alkyl-substituted vinyl POSS includes the following steps: (1) Derivatization reaction: Weigh 0.1g of alkyl-substituted vinyl POSS sample, add 1mL of tetrahydrofuran to dissolve it, then add 3-mercaptopropyltrimethoxysilane. The molar ratio of alkyl-substituted vinyl POSS to 3-mercaptopropyltrimethoxysilane is 1:17. Then add the initiator α-hydroxybenzophenone (the amount added is 0.5% of the total mass of alkyl-substituted vinyl POSS and 3-mercaptopropyltrimethoxysilane). After stirring evenly, react at 50℃ for 30min to obtain a derivatization reaction solution containing (3-(3-trimethoxysilylpropylthio)propyl)cage-shaped octameric silsesquioxane. (2) Sample pretreatment: After cooling the derivatized reaction solution obtained in step (1) to room temperature, it is diluted to 10 mL with tetrahydrofuran, filtered with a 0.22 μm organic phase filter membrane to remove insoluble impurities, and then accurately transferred 1 mL and diluted to 10 mL with the mobile phase to obtain the test solution. (3) High performance liquid chromatography detection: The test solution was injected into the high performance liquid chromatograph. The chromatographic conditions were as follows: C18 reversed phase column (column length 200 mm, column diameter 4.6 mm, packing particle size 5 μm); mobile phase was a mixture of acetonitrile and tetrahydrofuran (volume ratio 95:5), flow rate 1.0 mL / min; detection wavelength 213 nm; column temperature 36 ℃; injection volume 10 μL; record the chromatographic peak area of ​​the derivatives. (4) Content calculation: The content of the cage-like octameric silsesquioxane containing alkyl vinyls was calculated to be 81.90 wt% by normalization method.

[0042] Example 2 A method for determining the purity of alkyl-substituted vinyl POSS includes the following steps: (1) Derivatization reaction: Weigh 0.1g of alkyl-substituted vinyl POSS sample, add 1mL of tetrahydrofuran to dissolve it, then add 3-mercaptopropyltrimethoxysilane. The molar ratio of alkyl-substituted vinyl POSS to 3-mercaptopropyltrimethoxysilane is 1:17. Then add the initiator α-hydroxybenzophenone (the amount added is 0.5% of the total mass of alkyl-substituted vinyl POSS and 3-mercaptopropyltrimethoxysilane). After stirring evenly, react at 40℃ for 30min to obtain a derivatization reaction solution containing (3-(3-trimethoxysilylpropylthio)propyl)cage-shaped octameric silsesquioxane. (2) Sample pretreatment: After cooling the derivatized reaction solution obtained in step (1) to room temperature, it is diluted to 10 mL with tetrahydrofuran, filtered with a 0.22 μm organic phase filter membrane to remove insoluble impurities, and then accurately transferred 1 mL and diluted to 10 mL with the mobile phase to obtain the test solution. (3) High performance liquid chromatography detection: The test solution was injected into the high performance liquid chromatograph. The chromatographic conditions were as follows: C18 reversed phase column (column length 200 mm, column diameter 4.6 mm, packing particle size 5 μm); mobile phase was a mixture of acetonitrile and tetrahydrofuran (volume ratio 95:5), flow rate 1.0 mL / min; detection wavelength 213 nm; column temperature 36 ℃; injection volume 10 μL; record the chromatographic peak area of ​​the derivatives. (4) Content calculation: The content of the cage-like octameric silsesquioxane containing alkyl vinyls was calculated to be 65.95 wt% by normalization method.

[0043] Example 3 A method for determining the purity of alkyl-substituted vinyl POSS includes the following steps: (1) Derivatization reaction: Weigh 0.1g of alkyl-substituted vinyl POSS sample, add 1mL of tetrahydrofuran to dissolve it, then add 3-mercaptopropyltrimethoxysilane. The molar ratio of alkyl-substituted vinyl POSS to 3-mercaptopropyltrimethoxysilane is 1:10.2. Then add the initiator α-hydroxybenzophenone (the amount added is 0.5% of the total mass of alkyl-substituted vinyl POSS and 3-mercaptopropyltrimethoxysilane). After stirring evenly, react at 50℃ for 30min to obtain a derivatization reaction solution containing (3-(3-trimethoxysilylpropylthio)propyl)cage-shaped octameric silsesquioxane. (2) Sample pretreatment: After cooling the derivatized reaction solution obtained in step (1) to room temperature, it is diluted to 10 mL with tetrahydrofuran, filtered with a 0.22 μm organic phase filter membrane to remove insoluble impurities, and then accurately transferred 1 mL and diluted to 10 mL with the mobile phase to obtain the test solution. (3) High performance liquid chromatography detection: The test solution was injected into the high performance liquid chromatograph. The chromatographic conditions were as follows: C18 reversed phase column (column length 200 mm, column diameter 4.6 mm, packing particle size 5 μm); mobile phase was a mixture of acetonitrile and tetrahydrofuran (volume ratio 95:5), flow rate 1.0 mL / min; detection wavelength 213 nm; column temperature 36 ℃; injection volume 10 μL; record the chromatographic peak area of ​​the derivatives. (4) Content calculation: The content of the cage-like octameric silsesquioxane containing alkyl vinyls was calculated to be 69.14 wt% by normalization method.

[0044] Example 4 A method for determining the purity of alkyl-substituted vinyl POSS includes the following steps: (1) Derivatization reaction: Weigh 0.1g of alkyl-substituted vinyl POSS sample, add 1mL of tetrahydrofuran to dissolve it, then add 3-mercaptopropyltrimethoxysilane. The molar ratio of alkyl-substituted vinyl POSS to 3-mercaptopropyltrimethoxysilane is 1:17. Then add the initiator α-hydroxybenzophenone (the amount added is 0.1% of the total mass of alkyl-substituted vinyl POSS and 3-mercaptopropyltrimethoxysilane). After stirring evenly, react at 50℃ for 30min to obtain a derivatization reaction solution containing (3-(3-trimethoxysilylpropylthio)propyl)cage-shaped octameric silsesquioxane. (2) Sample pretreatment: After cooling the derivatized reaction solution obtained in step (1) to room temperature, it is diluted to 10 mL with tetrahydrofuran, filtered with a 0.22 μm organic phase filter membrane to remove insoluble impurities, and then accurately transferred 1 mL and diluted to 10 mL with the mobile phase to obtain the test solution. (3) High performance liquid chromatography detection: The test solution was injected into the high performance liquid chromatograph. The chromatographic conditions were as follows: C18 reversed phase column (column length 200 mm, column diameter 4.6 mm, packing particle size 5 μm); mobile phase was a mixture of acetonitrile and tetrahydrofuran (volume ratio 95:5), flow rate 1.0 mL / min; detection wavelength 213 nm; column temperature 36 ℃; injection volume 10 μL; record the chromatographic peak area of ​​the derivatives. (4) Content calculation: The content of the cage-like octameric silsesquioxane containing alkyl vinyls was calculated by normalization method to be 46.11 wt%.

[0045] Example 5 A method for determining the purity of alkyl-substituted vinyl POSS includes the following steps: (1) Derivatization reaction: Weigh 0.1g of alkyl-substituted vinyl POSS sample, add 2mL of tetrahydrofuran to dissolve, then add 3-mercaptopropyltrimethoxysilane. The molar ratio of alkyl-substituted vinyl POSS to 3-mercaptopropyltrimethoxysilane is 1:17. Then add the initiator α-hydroxybenzophenone (the amount added is 0.5% of the total mass of alkyl-substituted vinyl POSS and 3-mercaptopropyltrimethoxysilane). After stirring evenly, react at 50℃ for 30min to obtain a derivatization reaction solution containing (3-(3-trimethoxysilylpropylthio)propyl)cage-shaped octameric silsesquioxane. (2) Sample pretreatment: After cooling the derivatized reaction solution obtained in step (1) to room temperature, it is diluted to 10 mL with tetrahydrofuran, filtered with a 0.22 μm organic phase filter membrane to remove insoluble impurities, and then accurately transferred 1 mL and diluted to 10 mL with the mobile phase to obtain the test solution. (3) High performance liquid chromatography detection: The test solution was injected into the high performance liquid chromatograph. The chromatographic conditions were as follows: C18 reversed phase column (column length 200 mm, column diameter 4.6 mm, packing particle size 5 μm); mobile phase was a mixture of acetonitrile and tetrahydrofuran (volume ratio 95:5), flow rate 1.0 mL / min; detection wavelength 213 nm; column temperature 36 ℃; injection volume 10 μL; record the chromatographic peak area of ​​the derivatives. (4) Content calculation: The content of the cage-like octameric silsesquioxane containing alkyl vinyls was calculated to be 58.44 wt% by normalization method.

[0046] Comparative Example 1 A method for determining the purity of alkyl-substituted vinyl POSS includes the following steps: (1) Sample pretreatment: Accurately weigh 0.1g of alkyl-substituted vinyl POSS product and dilute to 10mL with tetrahydrofuran. Filter with a 0.22μm organic phase filter membrane to remove insoluble impurities. Then accurately transfer 1mL and dilute to 10mL with the mobile phase to obtain the sample solution to be tested. (2) Liquid chromatography detection: The sample solution to be tested was injected into the high performance liquid chromatograph. The chromatographic conditions were as follows: C18 reversed phase column (column length 200 mm, column diameter 4.6 mm, packing particle size 5 μm); mobile phase was a mixture of acetonitrile and tetrahydrofuran (volume ratio 95:5), flow rate 1.0 mL / min; detection wavelength 213 nm; column temperature 36 ℃; injection volume 10 μL; record the peak area of ​​the diffraction chromatogram. (3) Spectral results data analysis: The chromatographic peaks of alkyl-substituted vinyl POSS are not obvious and the response values ​​are low.

[0047] Figure 1 This is the high-performance liquid chromatogram of Example 1. Figure 2 This is the high-performance liquid chromatogram of Example 2. Figure 3This is the high-performance liquid chromatogram of Example 3. Figure 4 This is the high-performance liquid chromatogram of Example 4. Figure 5 This is the high-performance liquid chromatogram of Example 5. Figure 6 The high-performance liquid chromatogram of Comparative Example 1 shows that: Direct liquid chromatography (Comparative Example 1) was compared with derivatization reaction method (Example 1) under the same chromatographic conditions but without derivatization. The results showed that the chromatographic peak of alkyl-substituted vinyl POSS was not obvious and the response value was low, making accurate quantification impossible. Comparing Example 1 and Example 2, the test results show that when the temperature is below 50°C and the reaction time is the same, the impurity peak before the main peak increases, indicating that the reaction is not complete. Comparing Example 1 and Example 3, the test results show that when the amount of 3-mercaptopropyltrimethoxysilane is reduced, the impurity peak before the main peak increases with the same reaction time, indicating that the reaction is not complete. Comparing Example 1 and Example 4, the test results show that when the initiator dose is reduced and the reaction time is the same, the impurity peak before the main peak increases, indicating that the reaction is not complete. Comparing Example 1 and Example 5, increasing the solvent amount and decreasing the concentration resulted in an increase in the impurity peaks, indicating that the reaction was not complete. Figure 1 The lowest impurity peak and the lowest by-product peak before the main peak indicate that the reaction has proceeded completely and the detection effect is the best.

[0048] Example 6 Same as Example 1, except that the derivatization reaction temperature was 80°C and the content of alkyl vinyl cage-like octameric silsesquioxane was measured to be 77.86 wt%.

[0049] Example 7 Same as Example 1, except that the derivatization reaction temperature was 60°C and the content of alkyl vinyl cage-like octameric silsesquioxane was measured to be 78.95 wt%.

[0050] Example 8 Same as Example 1, except that the derivatization reaction temperature was 70°C and the content of alkyl vinyl cage-like octameric silsesquioxane was measured to be 79.88 wt%.

[0051] Example 9 Same as Example 1, except that the molar ratio of alkyl-substituted vinyl POSS to 3-mercaptopropyltrimethoxysilane was 1:18, and the content of alkyl vinyl cage-like octameric silsesquioxane was measured to be 80.64 wt%.

[0052] Example 10 Same as Example 1, except that the molar ratio of alkyl-substituted vinyl POSS to 3-mercaptopropyltrimethoxysilane was 1:19, and the content of alkyl vinyl cage-like octameric silsesquioxane was measured to be 80.12 wt%.

[0053] Example 11 Same as Example 1, except that the molar ratio of alkyl-substituted vinyl POSS to 3-mercaptopropyltrimethoxysilane was 1:20, and the content of alkyl vinyl cage-like octameric silsesquioxane was measured to be 79.34 wt%.

[0054] Example 12 Same as Example 1, except that the volume ratio of acetonitrile to tetrahydrofuran in the mobile phase was 70:30, and the content of alkyl vinyl cage-like octameric silsesquioxane was measured to be 74.99 wt%.

[0055] Example 13 Similar to Example 1, except that the amount of initiator used was 2.0% of the total mass of the alkyl vinyl cage-like octameric silsesquioxane and the mercapto compound, and the content of the alkyl vinyl cage-like octameric silsesquioxane was measured to be 78.59 wt%.

[0056] Example 14 Similar to Example 1, except that the amount of initiator used was 1.0% of the total mass of the alkyl vinyl cage-like octameric silsesquioxane and the mercapto compound, and the content of the alkyl vinyl cage-like octameric silsesquioxane was measured to be 79.64 wt%.

[0057] Example 15 Same as Example 1, except that the test wavelength was 210 nm and the content of alkyl vinyl cage-like octameric silsesquioxane was measured to be 76.55 wt%.

[0058] Example 16 Same as Example 1, except that the test wavelength was 230 nm and the content of alkyl vinyl cage-like octameric silsesquioxane was measured to be 75.48 wt%.

[0059] The comparative results show that the determination method of the present invention significantly improves the test sensitivity and accuracy through derivatization reaction, and solves the problem that existing methods cannot accurately determine the content of alkyl vinyl POSS.

[0060] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for detecting the content of cage-like octameric silsesquioxanes containing alkyl vinyl groups, characterized in that, Includes the following steps: The test sample is mixed with a mercapto compound and subjected to a click reaction to obtain a derivative; the test sample includes a cage-like octameric silsesquioxane containing alkyl vinyl groups. The derivative is mixed with a solvent to obtain the test solution; The test solution was subjected to high performance liquid chromatography to obtain the chromatographic peak area of ​​the test solution; The content of the alkyl vinyl cage-like octameric silsesquioxane containing alkyl vinyl groups is calculated based on the chromatographic peak area of ​​the test solution.

2. The content detection method according to claim 1, characterized in that, The thiol compound includes 3-mercaptopropyltrimethoxysilane.

3. The content detection method according to claim 1 or 2, characterized in that, The molar ratio of the cage-like octameric silsesquioxane containing alkyl vinyl groups to the mercapto compound is 1:17 to 1:

20.

4. The content detection method according to claim 1, characterized in that, The click reaction is carried out at a temperature of 50-80°C for 10-30 minutes.

5. The content detection method according to claim 1, characterized in that, The click reaction is carried out in an organic solvent, and the ratio of the alkyl vinyl cage-like octameric silsesquioxane to the organic solvent is 20-100 mg: 1 mL.

6. The content detection method according to claim 1, characterized in that, The click reaction is carried out under initiator conditions, wherein the amount of initiator is 0.1% to 2.0% of the total mass of the cage-like octameric silsesquioxane containing alkyl vinyl groups and the mercapto compound.

7. The content detection method according to claim 6, characterized in that, The initiator includes a photoinitiator and / or a thermal initiator.

8. The content detection method according to claim 7, characterized in that, The photoinitiator includes one or more of α-hydroxybenzophenone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and ethyl 2,4,6-trimethylbenzoyl phenylphosphonate.

9. The content detection method according to claim 1, characterized in that, The conditions for high-performance liquid chromatography (HPLC) detection include: a C18 reversed-phase column; a mobile phase of a mixture of acetonitrile and tetrahydrofuran, wherein the volume ratio of acetonitrile to tetrahydrofuran is 70:30 to 95:5; isocratic elution; a mobile phase flow rate of 0.8 to 1.2 mL / min; a detection wavelength of 210 to 230 nm; a column temperature of 25 to 40 °C; and an injection volume of 5 to 20 μL.

10. The content detection method according to claim 9, characterized in that, The C18 reversed-phase chromatographic column has a length of 150~250mm, a diameter of 4.6mm, and a packing particle size of 5μm.

Images