Ethoxy-containing polyhedral oligomeric silsesquioxane, preparation method and application thereof, and heat-resistant resin material

Abstract

The invention belongs to the technical field of flame-retardant materials, and particularly relates to ethyoxyl-containing polyhedral oligomeric silsesquioxane, a preparation method and application thereof and a heat-resistant resin material. The invention provides polyhedral oligomeric silsesquioxane containing ethyoxyl. The polyhedral oligomeric silsesquioxane containing ethyoxyl has a structure as shown in a formula I, the eight R groups comprise ethyl triethoxy silane and vinyl; the number of the ethyltriethoxysilane is n, and n is 1 to 8. The polyhedral oligomeric silsesquioxane provided by the invention simultaneously contains short-chain ethyoxyl and vinyl, has a trapezoidal POSS (Polyhedral Oligomeric Silsesquioxane) molecular skeleton, is good in product structure stability, and has excellent flame-retardant and heat-resistant effects. The ethyoxyl-containing polyhedral oligomeric silsesquioxane can be used as a resin cross-linking agent, forms a multiple cross-linked network in a resin system, effectively inhibits swinging and decomposition of terminal hydroxyl groups at low temperature, and can form POSS active free radicals with a quenching effect in a combustion process, so that the thermal stability and flame retardance of silicon resin are effectively improved. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of flame retardant materials, and particularly relates to a cage-shaped polysilsesquioxane containing ethoxy groups, a preparation method and application thereof, and a heat-resistant resin material. Background Art

[0002] Polyhedral Oligomeric Silsesquioxane (POSS) is a new type of organic-inorganic hybrid nanomaterial. Cage-shaped POSS is a nanomaterial with a core-shell structure containing organic-inorganic hybridization. Its internal inorganic framework serves as the core, which is a hexahedral cage structure composed of Si-O-Si or Si-O bonds. Each corner contains a Si atom, and each face is composed of Si-O-Si eight-membered rings, having strong structural symmetry. Multiple organic groups can be attached to each Si atom on the outside and extend into space. R can be H and active or inactive groups, such as epoxy groups, amino groups, carboxyl groups, alkenyl groups, alkyl groups, hydroxyl groups, aryl groups, etc.

[0003] Due to its silicon-oxygen-silicon cage structure, POSS has high stability and can have different physical and chemical properties by connecting different functional groups, thus attracting great research interest. Currently, the flame retardant and heat resistance properties of silicone rubber are insufficient to meet its applications in aerospace, home building, etc. Therefore, to solve the above problems, it is of great significance to study a POSS-based material with better heat resistance and flame retardancy. Summary of the Invention

[0004] The purpose of the present invention is to provide a cage-shaped polysilsesquioxane containing ethoxy groups, a preparation method and application thereof, and a heat-resistant resin material. The cage-shaped polysilsesquioxane containing ethoxy groups provided by the present invention has excellent flame retardant and heat resistance effects.

[0005] To achieve the above purpose, the present invention provides the following technical solutions:

[0006] The present invention provides a cage-shaped polysilsesquioxane containing ethoxy groups, having the structure shown in Formula I:

[0007]

[0008] In Formula I, the 8 Rs include ethyltriethoxysilane and vinyl; the number of ethyltriethoxysilane is n, the number of vinyl is 8 - n, and n is 1 - 8.

[0009] The present invention also provides a preparation method of the cage-shaped polysilsesquioxane containing ethoxy groups as described in the above technical solution, including the following steps:

[0010] Octavinyl octasilsequioxane, triethoxysilane, an addition catalyst and an organic solvent are mixed, and a hydrosilylation reaction is carried out to obtain the cage-shaped polysilsesquioxane containing ethoxy groups.

[0011] Preferably, the molar ratio of the octavinyl octasilsequioxane to the triethoxysilane is 1:1.05 to 9.2.

[0012] Preferably, the addition catalyst is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex.

[0013] Preferably, the mass ratio of the octavinyl octasilsequioxane to the addition catalyst is 1:0.001 to 0.1.

[0014] Preferably, the organic solvent includes one or more of aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents, nitrile solvents and furan solvents.

[0015] Preferably, the mass ratio of the octavinyl octasilsequioxane to the volume of the organic solvent is 1 g:5 to 20 mL.

[0016] Preferably, the temperature of the hydrosilylation reaction is 0 to 80 °C, and the reaction time is 2 to 12 h.

[0017] The present invention also provides the application of the cage-shaped polysilsesquioxane containing ethoxy groups described in the above technical solution or the cage-shaped polysilsesquioxane containing ethoxy groups obtained by the preparation method described in the above technical solution in heat-resistant flame-retardant materials.

[0018] The present invention also provides a heat-resistant resin material. Calculated by mass parts, the preparation raw materials include: 5 to 15 parts of resin, 0.5 to 2 parts of cross-linking agent, and 0.03 to 0.2 parts of curing agent; the cross-linking agent is the cage-shaped polysilsesquioxane containing ethoxy groups described in the above technical solution or the cage-shaped polysilsesquioxane containing ethoxy groups obtained by the preparation method described in the above technical solution.

[0019] The present invention provides a cage-shaped polysilsesquioxane containing ethoxy groups, which has the structure shown in Formula I; in Formula I, the 8 Rs include ethyltriethoxysilane and vinyl; the number of ethyltriethoxysilane is n, and the number of vinyl is 8 - n, where n is 1 to 8. The cage-shaped polysilsesquioxane provided by the present invention contains short-chain ethoxy groups and vinyl groups, has a ladder-shaped POSS molecular skeleton, the product has good structural stability, and at the same time has excellent flame-retardant and heat-resistant effects.

[0020] The cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups provided by the present invention can be used as a resin crosslinking agent to form a multiple crosslinking network in the resin system, effectively inhibiting the swing and decomposition of terminal hydroxyl groups at low temperatures, and forming POSS active free radicals with a quenching effect during the combustion process, effectively improving the thermal stability and flame retardancy of silicone resins. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0022] Figure 1 1H NMR spectrum of the cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups prepared in Example 1 1 ;

[0023] Figure 2 1H NMR spectrum of the cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups prepared in Example 1 29 29Si NMR spectrum;

[0024] Figure 3 1H NMR spectrum of the cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups prepared in Example 2 1 ;

[0025] Figure 4 1H NMR spectrum of the cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups prepared in Example 2 29 29Si NMR spectrum;

[0026] Figure 5 1H NMR spectrum of the cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups prepared in Example 3 1 ;

[0027] Figure 6 1H NMR spectrum of the cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups prepared in Example 3 29 29Si NMR spectrum;

[0028] Figure 7 1H NMR spectrum of the cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups prepared in Example 4 1 ;

[0029] Figure 8 1H NMR spectrum of the cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups prepared in Example 4 29 29Si NMR spectrum;

[0030] Figure 9FT-IR spectra of the cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups prepared in Examples 1 to 4;

[0031] Figure 10 Thermogravimetric analysis spectra of the heat-resistant resin materials prepared in Examples 5 to 8 and the resin material prepared in Comparative Example 1. Detailed implementation manners

[0032] The present invention provides a cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups, having the structure shown in Formula I:

[0033]

[0034] In Formula I, the 8 Rs include ethyltriethoxysilane and vinyl; the number of ethyltriethoxysilane is n, the number of vinyl is 8 - n, and n is 1 to 8.

[0035] In the present invention, n is 1 to 8, and in specific embodiments, it can be 2, 4, 6 or 8.

[0036] The cage-shaped polyhedral oligomeric silsesquioxane provided by the present invention contains both short-chain ethoxy groups and vinyl groups, has a ladder-shaped POSS molecular skeleton, the product has good structural stability, and at the same time has excellent flame retardant and heat resistance effects. The cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups can be used as a resin cross-linking agent to form a multiple cross-linked network in the resin system, effectively inhibiting the swing and decomposition of terminal hydroxyl groups at low temperatures, and can form POSS active free radicals with a quenching effect during the combustion process, effectively improving the thermal stability and flame retardancy of silicone resins.

[0037] The present invention also provides a preparation method of the cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups according to the above technical solution, including the following steps:

[0038] Octavinyl octasilsesquioxane, triethoxysilane, an addition catalyst and an organic solvent are mixed to carry out a hydrosilylation reaction to obtain the cage-shaped polyhedral oligomeric silsesquioxane containing ethoxy groups.

[0039] In the present invention, unless otherwise specified, all raw material components are commercially available products well-known to those skilled in the art.

[0040] In the present invention, the molar ratio of octavinyl octasilsesquioxane to triethoxysilane is 1:1.05 to 9.2; specifically, it can be 1:(1.05 to 1.15)×n, where n is the addition number of triethoxysilane. In specific embodiments, it can be 1:2.1, 1:4.2, 1:6.3 or 1:8.4. In the present invention, ethoxy groups can be used as cross-linking groups, and the multiple cross-linked network and the self-POSS rigid structure generated can effectively improve the heat resistance and flame retardancy of silicone rubber. At the same time, vinyl groups also have flame retardant properties, and different amounts of ethoxy groups have an impact on the cross-linked structure and flame retardant properties.

[0041] In the present invention, the addition catalyst is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex, namely Karstedt catalyst; the mass ratio of the octavinylsilsesquioxane to the addition catalyst is 1:0.001-0.1, and in specific embodiments, it can be 1:0.01, 1:0.05 or 1:0.08.

[0042] In the present invention, the organic solvent includes one or more of aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents, nitrile solvents and furan solvents; the aromatic hydrocarbon solvents include toluene and / or benzene; the halogenated hydrocarbon solvents include dichloromethane and / or chloroform; the amide solvents include dimethylformamide; the nitrile solvents include acetonitrile; the furan solvents include tetrahydrofuran; in specific embodiments, the organic solvent can be dichloromethane or toluene; the mass of the octavinylsilsesquioxane and the volume ratio of the organic solvent is 1 g:5-20 mL, and in specific embodiments, it can be 1 g:8 mL, 1 g:10 mL, 1 g:12 mL or 1 g:15 mL.

[0043] In the present invention, the temperature of the hydrosilylation reaction is 0-80 °C, and in specific embodiments, it can be 10 °C, 25 °C, 40 °C or 60 °C; the reaction time is 2-12 h, and in specific embodiments, it can be 3 h, 5 h, 8 h or 10 h.

[0044] In the present invention, after the hydrosilylation reaction, quenching, solid-liquid separation and solvent removal are sequentially carried out; the quenching reagent is activated carbon and / or silica powder; the mass ratio of the octavinylsilsesquioxane to the quenching reagent is 100:1-10, and in specific embodiments, it can be 1:0.038 or 1:0.05; the quenching method is to add the quenching reagent and stir; the stirring time is 10-60 min, and in specific embodiments, it can be 20 min or 40 min; the solid-liquid separation can be suction filtration; the solvent removal can be vacuum evaporation; the present invention has no special limitation on the processes of the suction filtration and vacuum evaporation, and the methods well-known to those skilled in the art can be used. The role of the solid-liquid separation in the present invention is to separate the quenching reagent.

[0045] The preparation method provided by the present invention can prepare POSS products containing different proportions of functional groups by controlling the raw material ratio. It has the characteristics of mild reaction conditions, good repeatability, high yield, short cycle and simple operation, and is suitable for large-scale production.

[0046] The present invention also provides the application of the silsesquioxane containing ethoxy groups described in the above technical solution or the silsesquioxane containing ethoxy groups obtained by the preparation method described in the above technical solution in heat-resistant flame-retardant materials.

[0047] In the present invention, the heat-resistant flame-retardant material can be a heat-resistant flame-retardant resin material; the silsesquioxane containing ethoxy groups can be used as a cross-linking agent for the heat-resistant flame-retardant resin material; the heat-resistant flame-retardant material can be used for aerospace materials, automotive materials or mechanical materials; the heat-resistant flame-retardant material can be used as a high-temperature resistant coating or a sealing ring.

[0048] The present invention also provides a heat-resistant resin material. Calculated by mass parts, the preparation raw materials include: 5-15 parts of resin, 0.5-2 parts of cross-linking agent and 0.03-0.2 parts of curing agent; the cross-linking agent is the silsesquioxane containing ethoxy groups described in the above technical solution or the silsesquioxane containing ethoxy groups obtained by the preparation method described in the above technical solution.

[0049] In the present invention, the preparation raw materials of the heat-resistant resin material include 5-15 parts of resin. In a specific embodiment, it can be 10 parts; the resin is a condensation type silicone resin. In a specific embodiment, it can be methyl silicone resin or methyl phenyl silicone resin.

[0050] Based on the mass parts of the resin; the preparation raw materials of the heat-resistant resin material further include 0.5-2 parts of cross-linking agent. In a specific embodiment, it can be 1 part.

[0051] Based on the mass parts of the resin; the preparation raw materials of the heat-resistant resin material further include 0.03-0.2 parts of curing agent. In a specific embodiment, it can be 0.08 or 0.15; the curing agent includes an organotin catalyst. In a specific embodiment, it can be dibutyltin dilaurate or dibutyltin isooctoate.

[0052] In the present invention, the preparation method of the heat-resistant resin material includes the following steps:

[0053] Mix the resin, cross-linking agent and curing agent, and carry out curing to obtain the heat-resistant resin material.

[0054] In the present invention, the mixing is stirring; the stirring time is 15-30 min. In a specific embodiment, it can be 20 min.

[0055] In the present invention, a vacuum pumping treatment is also included before curing; the time of the vacuum pumping treatment is 10-20 min. In a specific embodiment, it can be 10 min; the curing temperature is 0-60 °C. In a specific embodiment, it can be 25 °C; the curing time is 3-7 d. In a specific embodiment, it can be 3 d.

[0056] The heat-resistant resin material provided by the present invention is easy to prepare, easy to process, has a high yield, has high heat resistance and high flame retardancy, and is applicable to fields such as automobiles, furniture, building materials, etc.

[0057] In order to further illustrate the present invention, the cage-shaped polysilsesquioxane containing ethoxy groups provided by the present invention, its preparation method and application, and the heat-resistant resin material will be described in detail below in conjunction with the accompanying drawings and embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0058] Example 1

[0059] 13 g of octavinyl octasilsesquioxane, 6.74 g of triethoxysilane and 100 mL of dichloromethane were added to a 250 mL two-necked flask equipped with a three-way valve with a nitrogen balloon and a reverse rubber stopper, and the inside of the flask was filled with nitrogen using an oil pump.

[0060] 0.5 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex solution (2% wt) was added, and the reaction was carried out at 25 °C for 8 h.

[0061] The reaction was stopped, 0.5 g of activated carbon was added, and stirring was continued for 0.5 h. The mixed solution was obtained by suction filtration, and the solvent was removed by evaporation under reduced pressure to obtain 18.92 g of a colorless transparent liquid, that is, the cage-shaped polysilsesquioxane product containing ethoxy groups, and the addition number of triethoxysilane in its structure was 2, denoted as 2KPOSS, and the yield was 95.8%. Figures 1 to 2 Respectively, the 1 HNMR and 29 Si NMR spectra of 2KPOSS.

[0062] From Figure 1 it can be seen that the peak corresponding to the vinyl group at 6 ppm becomes smaller, and the peak at 1.19 ppm corresponds to the H on the carbon atom connected to the ethoxysilane. The area ratio of the two is about 1:1, indicating that triethoxysilane undergoes an addition reaction with the vinyl group in a ratio of 1:4.

[0063] From Figure 2 it can be seen that the two peaks at -65 ppm and -80 ppm correspond to the silicon atoms on the silicon oxygen cage, and their chemical shifts are different due to reactions with different raw materials. The quantitative silicon spectrum indicates that triethoxysilane undergoes an addition reaction with the vinyl group in a ratio of 1:4.

[0064] Example 2

[0065] 10 g of octavinyl octasilsesquioxane, 10.38 g of triethoxysilane and 80 mL of toluene were added to a 250 mL two-necked flask equipped with a three-way valve with a nitrogen balloon and a reverse rubber stopper, and the inside of the flask was filled with nitrogen using an oil pump.

[0066] Add 0.5 mL of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex and react at 60 °C for 3 h.

[0067] Stop the reaction, add 0.5 g of silica gel powder, continue stirring for 0.5 h, filter by suction to obtain a mixed solution, remove the solvent under reduced pressure, and obtain 19.33 g of a colorless transparent liquid, which is a cage-shaped polysilsesquioxane product containing ethoxy groups. The addition number of triethoxysilane in its structure is 4, denoted as 4KPOSS, and the yield is 94.8%. Figures 3 to 4 Respectively for 4KPOSS 1 HNMR and 29 SiNMR spectra.

[0068] From Figure 3 It can be seen that the peak corresponding to the vinyl group at 6 ppm becomes smaller, and the peak at 1.19 ppm corresponds to the H on the carbon atom connected to the ethoxysilane. The area ratio of the two is about 1:3, indicating that triethoxysilane undergoes an addition reaction with the vinyl group in a ratio of 1:2.

[0069] From Figure 4 It can be seen that the two peaks at -65 ppm and -80 ppm correspond to the silicon atoms on the silicon oxygen cage, and their chemical shifts are different due to reactions with different raw materials. Quantitative silicon spectroscopy shows that triethoxysilane undergoes an addition reaction with the vinyl group in a ratio of 1:2.

[0070] Example 3

[0071] Add 10 g of octavinyl octasilsesquioxane, 15.66 g of triethoxysilane, and 110 mL of dichloromethane to a 250 mL two-necked flask equipped with a three-way valve with a nitrogen balloon and a reverse rubber stopper, and use an oil pump to fill the flask with nitrogen.

[0072] Add 1 mL of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex and react at 10 °C for 12 h.

[0073] Stop the reaction, add 0.5 g of silica gel powder, continue stirring for 0.5 h, filter by suction to obtain a mixed solution, remove the solvent under reduced pressure, and obtain 23.76 g of a colorless transparent liquid, which is a cage-shaped polysilsesquioxane product containing ethoxy groups. The addition number of triethoxysilane in its structure is 6, denoted as 6KPOSS, and the yield is 92.6%. Figures 5 to 6 Respectively for 6KPOSS 1 HNMR and 29 SiNMR spectra.

[0074] From Figure 5It can be seen that the peak corresponding to the vinyl group at 6 ppm becomes smaller, and the peak at 1.19 ppm corresponds to the H on the carbon atom connected to the ethoxysilane. The area ratio of the two is about 1:1, indicating that triethoxysilane undergoes an addition reaction with the vinyl group in a ratio of 3:4.

[0075] It can be seen from Figure 6 that the two peaks at -65 ppm and -80 ppm correspond to the silicon atoms on the silicon-oxygen cage, and their chemical shifts are different due to reactions with different raw materials. Quantitative silicon NMR shows that triethoxysilane undergoes an addition reaction with the vinyl group in a ratio of 3:4.

[0076] Example 4

[0077] 10 g of octavinyl octasilasesquioxane, 20.79 g of triethoxysilane and 80 mL of toluene were added to a 250 mL two-necked flask equipped with a three-way valve with a nitrogen balloon and a rubber stopper with a reversed opening, and the flask was filled with nitrogen using an oil pump.

[0078] 1.0 mL of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex was added, and the reaction was carried out at 60 °C for 3 h.

[0079] The reaction was stopped, 0.5 g of silica powder was added, and stirring was continued for 0.5 h. The mixture was filtered to obtain a mixed solution, and the solvent was removed under reduced pressure to obtain 29.10 g of a colorless transparent liquid, i.e., a cage-shaped polysilsesquioxane product containing ethoxy groups, in which the addition number of triethoxysilane is 8, denoted as 8KPOSS, and the yield is 94.8%. Figures 7 to 8 Respectively, the 1 HNMR and 29 SiNMR spectra of 8KPOSS.

[0080] It can be seen from Figure 7 that the peak corresponding to the vinyl group at 6 ppm completely disappears, indicating that triethoxysilane undergoes an addition reaction with the vinyl group in a ratio of 1:1.

[0081] It can be seen from Figure 8 that the peak at -80 ppm completely disappears, indicating that triethoxysilane undergoes an addition reaction with the vinyl group in a ratio of 1:1.

[0082] Figure 9 FT-IR spectra of the cage-shaped polysilsesquioxanes containing ethoxy groups obtained in Examples 1 to 4 are shown. In the figure, OVS is octavinyl octasilasesquioxane. It can be seen from Figure 9 that with the change of the feeding ratio, the intensities of the characteristic peaks of the vinyl group at 1604 cm -1 and 3066 cm -1 decrease until they disappear, and the characteristic peaks of the methylene group at 2885 cm -1 and 2973 cm -1 and the benzene ring peak at 1619 cm-1 The strengths increase and decrease reciprocally, indicating that the double-bond addition ratio in octavinylsilsesquioxane will vary with the feed ratio to obtain the target product.

[0083] Example 5

[0084] Take 10 g of methyl silicone resin, 1 g of 2K POSS obtained in Example 1, and 0.08 g of dibutyltin dilaurate in a beaker, and stir with a paddle for 20 min until evenly mixed.

[0085] Put the beaker into a vacuum oven, evacuate at room temperature for 10 min, take out the sample, pour it into a mold, and cure at room temperature for 3 d to obtain a heat-resistant resin material, denoted as SR-2KPOSS.

[0086] Example 6

[0087] Prepare the heat-resistant resin material according to the scheme provided in Example 5, except that 4K POSS obtained in Example 2 is used to replace 2K POSS, and the obtained heat-resistant resin material is denoted as SR-4KPOSS.

[0088] Example 7

[0089] Prepare the heat-resistant resin material according to the scheme provided in Example 5, except that 6K POSS obtained in Example 3 is used to replace 2K POSS, and the obtained heat-resistant resin material is denoted as SR-6KPOSS.

[0090] Example 8

[0091] Prepare the heat-resistant resin material according to the scheme provided in Example 5, except that 8K POSS obtained in Example 4 is used to replace 2K POSS, and the obtained heat-resistant resin material is denoted as SR-8KPOSS.

[0092] Comparative Example 1

[0093] Prepare the resin material according to the scheme provided in Example 5, except that tetraethoxysilane (TEOS) is used to replace 2K POSS, and the obtained resin material is denoted as SR.

[0094] Test Example

[0095] Perform thermogravimetric analysis on the resin materials obtained in Examples 5 to 8 and Comparative Example 1, and test the limiting oxygen index. The thermogravimetric analysis spectra of the resin materials obtained in Examples 5 to 8 and Comparative Example 1 under nitrogen are shown in Figure 10 .

[0096] From Figure 10It can be seen that, compared with the resin material obtained in Comparative Example 1, the heat-resistant resin materials obtained in Examples 5 to 8 have higher thermal stability, the decomposition rate is greatly reduced in the range of 350 to 550 °C, and the residual carbon mass increases with the decrease of the substituent group. Compared with the resin material obtained in Comparative Example 1, the limiting oxygen index of the heat-resistant resin material obtained in Example 5 increases from 24.0% to 28.5%

[0097] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention, rather than all embodiments. Other embodiments can also be obtained based on these embodiments without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A cage-shaped polysilsesquioxane containing an ethoxy group, characterized in that: It has the structure shown in formula I: In formula I, 8 Rs include ethyltriethoxysilane and vinyl groups; the number of the ethyltriethoxysilane groups is n, the number of the vinyl groups is 8-n, and n is 1 to 8.

2. The method for preparing the ethoxy-containing cage-shaped polysilsesquioxane according to claim 1, characterized in that: The following steps are involved: Octavinyloctasilsesquioxane, triethoxysilane, an addition catalyst and an organic solvent are mixed and subjected to a hydrosilylation reaction to obtain the cage-shaped polysilsesquioxane containing ethoxy groups.

3. The preparation method according to claim 2, characterized in that: The molar ratio of octavinyloctasilsesquioxane to triethoxysilane is 1:1.05-9.

2.

4. The preparation method according to claim 2, characterized in that: The addition catalyst is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex.

5. The preparation method according to claim 2 or 4, characterized in that: The mass ratio of the octavinyl octasilsesquioxane to the addition catalyst is 1:0.001-0.

1.

6. The preparation method according to claim 2, characterized in that: The organic solvent includes one or more of aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents, nitrile solvents and furan solvents.

7. The preparation method according to claim 2 or 6, characterized in that: The mass ratio of the octavinyloctasilsesquioxane to the volume ratio of the organic solvent is 1 g:5 to 20 mL.

8. The preparation method according to claim 2, characterized in that: The temperature of the hydrosilylation reaction is 0 to 80° C., and the reaction time is 2 to 12 hours.

9. Use of the cage-shaped polysilsesquioxane containing ethoxy groups according to claim 1 or the cage-shaped polysilsesquioxane containing ethoxy groups obtained by the preparation method according to any one of claims 2 to 8 in heat-resistant and flame-retardant materials.

10. A heat-resistant resin material, characterized in that: The raw materials for preparation include, by weight: 5 to 15 parts of resin, 0.5 to 2 parts of cross-linking agent and 0.03 to 0.2 parts of curing agent; the cross-linking agent is the ethoxy-containing cage-shaped polysilsesquioxane according to claim 1 or the ethoxy-containing cage-shaped polysilsesquioxane obtained by the preparation method according to any one of claims 2 to 8.

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