A POSS hybrid zirconium-containing phenylsilicone resin and a method of making the same

Abstract

The application discloses a POSS hybrid zirconium-containing phenyl silicone resin, which is prepared by hydrolysis-polycondensation of a zirconium-containing phenyl silicone resin and POSS. The application also discloses a preparation method of the POSS hybrid zirconium-containing phenyl silicone resin. The prepared POSS hybrid zirconium-containing phenyl silicone resin has excellent high-temperature resistance, the initial decomposition temperature is 542.1 DEG C, the temperature at 10% decomposition is 729.7 DEG C, and the residual rate at 800 DEG C is as high as 88.05%, so that the POSS hybrid zirconium-containing phenyl silicone resin has a wide application prospect in the preparation of thermal protection coatings.

Description

Technical Field

[0001] This invention relates to the field of organosilicon resin technology, specifically to a POSS hybrid zirconium-containing phenyl silicone resin and its preparation method. Background Technology

[0002] Organosilicon resin is a high-performance, high-temperature resistant material, possessing the dual characteristics of a cross-linked semi-inorganic polymer with an inorganic Si-O backbone and organic side groups, as well as an organic-inorganic material. Compared to homologous carbon-based polymers, it exhibits better high-temperature resistance. Compared to other materials, it also possesses many excellent properties, such as weather resistance, radiation resistance, corrosion resistance, insulation, water resistance, and oxidation resistance. When used in combination with certain heat-resistant fillers, it exhibits ablation and melting properties at high temperatures. Due to its excellent properties, organosilicon resin is widely used in adhesives, sealants, and thermal insulation coatings in the electronics and aerospace fields. However, with the rapid development of industries such as machinery, chemicals, and defense, and the deterioration of working environments such as rising temperatures and radiation, ordinary organosilicon resin can no longer meet practical needs. Therefore, it is necessary to further improve the thermal stability of organosilicon resin. Cured zirconium-containing phenyl silicone resin still contains a large number of Si-OH groups. Numerous terminal hydroxyl groups exist at the ends, and under thermo-oxidative conditions, the Si-OH groups at the ends of the organosilicon resin undergo "biting back." Polyhedral oligomeric silsesquioxanes (POSS) show great potential for improving the thermal stability of polymers due to their unique intramolecular hybridization, designable structure and good thermal stability.

[0003] The paper "Study on POSS-Hybridized Zirconium-Containing Phenyl Silicone Resin" published by Shaanxi University of Science and Technology discloses the modification of zirconium-containing phenyl silicone resin using POSS. However, in this experiment, the zirconium-containing phenyl silicone resin was prepared by hydrolytic co-condensation of zirconium oxychloride (ZrOCl2·8H2O) with polyfunctional siloxane monomers (PTES and DPDMS). Zirconium oxychloride is an inorganic salt, which has incompatibility problems when reacting with organic compounds, making it difficult for the reaction to proceed completely. In addition, the experimental product contains chloride ions, which are difficult to remove, and will significantly affect the service life and thermal stability of the organosilicon resin. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a POSS hybrid zirconium-containing phenyl organosilicon resin with excellent thermal stability.

[0005] Another object of the present invention is to provide a method for preparing the POSS hybrid zirconium-containing phenyl organosilicon resin.

[0006] To achieve the above-mentioned objectives of this invention, the technical solution adopted by this invention is: a POSS hybrid zirconium-containing phenyl silicone resin, which is prepared by hydrolysis-condensation reaction of POSS and zirconium-containing organosilicon resin.

[0007] Preferably, the POSS hybrid zirconium-containing phenyl silicone resin is made from components comprising the following mass percentages:

[0008] Zirconium-containing phenyl silicone resin 90-99%

[0009] POSS 1-10%.

[0010] The zirconium-containing phenyl organosilicon resin is a zirconium-butanol hybrid phenyl organosilicon resin prepolymer, a zirconium-isobutanol hybrid phenyl organosilicon resin prepolymer, and / or a zirconium-tert-butanol hybrid phenyl organosilicon resin prepolymer.

[0011] The POSS can be heptaphenyl cage-like polysilsesquioxane trisilanol (phenyl T7-POSS), heptaisobutyl cage-like polysilsesquioxane trisilanol (isobutyl T7-POSS), and / or heptamethyl cage-like polysilsesquioxane (dimethyl T7-POSS). Phenyl T7-POSS prepared by Beijing Institute of Technology with a purity greater than 99.5% can be selected, or isobutyl T7-POSS and / or dimethyl T7-POSS produced by Angxing New Carbon Materials Changzhou Co., Ltd. with a purity greater than 98.5%.

[0012] A method for preparing a POSS hybrid zirconium-containing phenyl silicone resin includes the following steps:

[0013] a. Dissolve zirconium-containing phenyl organosilicon resin in a solvent to prepare a zirconium-containing phenyl organosilicon resin solution, wherein the concentration of zirconium-containing phenyl organosilicon resin is 0.02-0.5 g / mL;

[0014] b. Dissolve POSS in a zirconium-phenyl organosilicon resin solution;

[0015] c. Then add 0.1-2 wt% curing aid and seal the reactor;

[0016] d. Stir the reaction at 10–100℃ for 6–24 hours;

[0017] e. Under conditions of 50 to 100°C and -0.01 to -0.1 MPa, the solvent and residual water in the system are removed by vacuum distillation to obtain POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer.

[0018] f. Place the POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer in a vacuum chamber and allow it to stand and defoam.

[0019] g. After defoaming, remove it from the vacuum chamber and place it at room temperature for 12-48 hours. Then, cure it in an oven at 50-120℃ for 1-10 hours to obtain POSS hybrid zirconium-containing phenyl organosilicon resin.

[0020] In step a, the solvent is one of ethanol, methanol, n-butanol, isopropanol, or toluene.

[0021] In step c, the curing aid is either stannous octoate or dibutyltin dilaurate.

[0022] A method for preparing a POSS hybrid zirconium-containing phenyl silicone resin includes the following steps:

[0023] a. Dissolve 1-10g of zirconium-containing phenyl organosilicon resin in 20-50mL of solvent to prepare a zirconium-containing phenyl organosilicon resin solution;

[0024] b. Weigh 0.01-1g of POSS and dissolve it in a zirconium-phenyl organosilicon resin solution;

[0025] c. Then add 0.1-2 wt% curing aid and seal the reactor;

[0026] d. Stir the reaction at 10–100℃ for 6–24 hours;

[0027] e. Under conditions of 50 to 100°C and -0.01 to -0.1 MPa, the solvent and residual water in the system are removed by vacuum distillation to obtain POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer.

[0028] f. Place the POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer in a vacuum chamber and allow it to stand and defoam.

[0029] g. After defoaming, remove it from the vacuum chamber and place it at room temperature for 12-48 hours. Then, cure it in an oven at 50-120℃ for 1-10 hours to obtain POSS hybrid zirconium-containing phenyl organosilicon resin.

[0030] Preferably, in step a, the amount of zirconium-containing phenyl silicone resin added is 1g, and the amount of solvent added is 20mL.

[0031] Preferably, in step a, the solvent is one of ethanol, methanol, n-butanol, isopropanol, or toluene.

[0032] Preferably, in step b, the amount of POSS added is 0.05g.

[0033] Preferably, in step c, the amount of curing agent added is 0.2 wt%.

[0034] Preferably, in step d, the reaction temperature is 70°C and the reaction time is 12 hours.

[0035] Preferably, in step e, the temperature of the vacuum distillation is 50°C and the pressure of the vacuum distillation is -0.1 MPa.

[0036] Preferably, in step f, the defoaming temperature is 20°C and the defoaming time is 10 min.

[0037] Preferably, in step g, the time spent at room temperature is 24 hours, the curing temperature is 80°C, and the curing time is 4 hours.

[0038] Compared with the prior art, the present invention has the following outstanding effects:

[0039] (1) Based on the organic alcohol zirconium hybrid zirconium-containing phenyl silicone resin, a convenient, stable and efficient hydrolysis-condensation method was adopted to successfully prepare POSS hybrid zirconium-containing phenyl silicone resin. This method can avoid cumbersome reactions and the preparation process is simple and easy to operate. Moreover, the product contains no chloride ions, which significantly improves the thermal stability of the silicone resin.

[0040] (2) By utilizing the unique intramolecular hybridization of POSS as a limiting point to suppress the thermal vibration of organosilicon resin molecular chains, it can be grafted into zirconium-containing organosilicon resins to suppress random breakage reactions in the main chain.

[0041] In summary, POSS-hybrid zirconium-containing phenyl silicone resins exhibit excellent thermal oxidation stability. When the content of T7-POSS is 1 wt%, the system's T 5％ T 10％ The temperature and the cumulative remaining mass both reached their maximum values, at 542.1℃, 729.7℃, and 88.05%, respectively. Attached Figure Description

[0042] Figure 1 The infrared spectrum of the POSS hybrid zirconium-containing phenyl organosilicon resin prepared in Example 1 is shown below.

[0043] Figure 2 The infrared spectra of the POSS hybrid zirconium-containing phenyl organosilicon resin prepared in Example 1 before and after heat treatment are shown below.

[0044] Figure 3 The XRD pattern of the POSS hybrid zirconium-containing phenyl organosilicon resin prepared in Example 1 is shown below.

[0045] Figure 4 SEM image of the POSS hybrid zirconium-containing phenyl organosilicon resin prepared in Example 1;

[0046] Figure 5 The TGA curve of the POSS hybrid zirconium-containing phenyl organosilicon resin obtained in Example 1 under a nitrogen atmosphere;

[0047] Figure 6The DTG curve of the POSS hybrid zirconium-containing phenyl organosilicon resin prepared in Example 1 under a nitrogen atmosphere. Specific implementation methods

[0048] The present invention will be further described below with reference to specific embodiments and accompanying drawings. It should be noted that the embodiments do not constitute a limitation on the scope of protection of the present invention.

[0049] The zirconium-containing phenyl organosilicon resin of the present invention is made from components comprising the following molar percentages:

[0050]

[0051] The methylethoxysilane is methyltriethoxysilane and / or dimethyldiethoxysilane. The phenylsilane is trimethoxyphenylsilane and / or methylphenyldimethoxysilane. The cyclosiloxane is 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxycyclosiloxane. 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrocyclosiloxane of type W306017 produced by Shanghai Aladdin Biochemical Technology Co., Ltd., with a purity of 97%, can be used. The organic zirconium alcohol is zirconium n-butoxide, zirconium tert-butoxide, and / or zirconium isobutoxide.

[0052] The preparation method of the zirconium-containing phenyl organosilicon resin includes the following steps:

[0053] a. Dissolve the organic alcohol zirconium in the first solvent to prepare a zirconium-containing solution;

[0054] b. Dissolve hydrochloric acid in deionized water to prepare a hydrochloric acid solution with a pH value of 1 to 6;

[0055] c. Add a second solvent to the reaction vessel and add hydrochloric acid solution to prepare a reaction mixture;

[0056] d. Add methylethoxysilane, phenylsilane and cyclosiloxane dropwise to the reaction mixture;

[0057] e. Stir and mix at 10–30°C for 1–3 minutes;

[0058] f. Use a peristaltic pump to slowly add the zirconium-containing solution to the reactants obtained in step e;

[0059] g. Stir the reaction at a temperature of 10–100℃ for 1–6 hours;

[0060] h. After the reaction is complete, add an organic amine compound dropwise to the reaction mixture to neutralize the excess hydrochloric acid in the system, and filter to remove the solid salt produced.

[0061] i. Under conditions of temperature of 50 to 100°C and pressure of -0.01 to -0.1 MPa, the solvent, residual water and excess organic amine compounds in the system are removed by vacuum distillation to obtain a zirconium-containing phenyl organosilicon resin prepolymer.

[0062] j. Place the zirconium-containing phenyl organosilicon resin prepolymer in a vacuum chamber and allow it to stand and defoam.

[0063] k. After defoaming, the zirconium-containing phenyl silicone resin prepolymer is taken out of the vacuum chamber and placed in a muffle furnace for stepwise temperature curing.

[0064] Preferably, in step a, the first solvent is one of ethanol, methanol, n-butanol, or isopropanol.

[0065] Preferably, in step a, the amount of the first solvent added is twice the molar amount of the organic zirconium alcohol.

[0066] Preferably, in step c, the second solvent is one of ethanol, methanol, tetrahydrofuran, n-butanol, and isopropanol.

[0067] Preferably, in step c, the amount of the second solvent added is equal to the mass of the silane, wherein the silane is the total mass of methylethoxysilane, phenylsilane, and / or cyclosiloxane.

[0068] Preferably, in step c, the amount of hydrochloric acid solution added is equal to the molar amount of alkoxy groups in silane and organic zirconium alcohol, wherein the silane is the sum of alkoxy groups in methylethoxysilane, phenylsilane and cyclosiloxane.

[0069] Preferably, in step h, the organic amine compound is one of ethylenediamine, cyclohexylamine, or triethanolamine.

[0070] Preferably, in step k, the stepped heating program is 80℃ x 1h (continuously at 80℃ for 1 hour), 100℃ x 1h, 130℃ x 2h, 180℃ x 2h, 220℃ x 2h, and 300℃ x 1h. During the curing process, small molecule substances are generated. Stepped heating solves the problem that directly heating to 300℃ would cause a large number of bubbles to be generated when these small molecules vaporize and leave the silicone resin, affecting the mechanical properties of the silicone resin. Furthermore, if the temperature is below 300℃, incomplete curing will occur. The stirring speed is 50-500 rpm.

[0071] Example 1:

[0072] A method for preparing a POSS hybrid zirconium-containing phenyl silicone resin includes the following steps:

[0073] a. Dissolve 1g of n-butanol zirconium hybrid phenyl organosilicon resin prepolymer in 20mL of toluene to prepare a zirconium-containing phenyl organosilicon resin solution.

[0074] b. Weigh 0.05g of heptaphenyl cage-like polysilsesquioxane trisilol (phenyl T7-POSS) and dissolve it in a zirconium-containing phenyl organosilicon resin solution;

[0075] c. Then add 0.2 wt% of stannous octoate to the solution obtained in step b, and seal the reactor;

[0076] d. Stir the reaction at 70℃ for 12 hours;

[0077] e. Under conditions of 50℃ and -0.1MPa, the solvent and residual water in the system are removed by vacuum distillation to obtain POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer.

[0078] f. Place the POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer in a vacuum chamber and allow it to stand for defoaming at 20°C for 10 minutes.

[0079] g. After defoaming, the POSS hybrid zirconium-containing phenyl silicone resin prepolymer is taken out of the vacuum chamber, placed at room temperature for 24 hours, and then cured in an oven at 80°C for 4 hours to obtain the POSS hybrid zirconium-containing phenyl silicone resin.

[0080] The preparation method of the n-butanol zirconium hybrid phenyl organosilicon resin prepolymer includes the following steps:

[0081] a. Dissolve 0.0037 mol of zirconium n-butoxide in 0.074 mol of ethanol to prepare a zirconium-containing solution;

[0082] b. Measure 10 mL of hydrochloric acid, dissolve it in deionized water, and prepare a hydrochloric acid solution with a pH of 2.

[0083] c. Add 74.12 g of methanol to the reaction vessel and add 1.123 mol of hydrochloric acid solution to prepare the reaction mixture;

[0084] d. Add dropwise 0.16 mol methyltriethoxysilane, 0.0025 mol dimethyldiethoxysilane, 0.035 mol 1,3,5,7-tetramethyl1,3,5,7-tetrahydroxycyclosiloxane and 0.175 mol methylphenyldimethoxysilane to the reaction mixture;

[0085] e. Stir and mix at 20°C for 2 minutes;

[0086] f. Using a peristaltic pump, slowly add the zirconium-containing solution to the reactants obtained in step e at a speed of 20 rpm;

[0087] g. Stir the reaction at 25°C for 4 hours;

[0088] h. After the reaction is complete, add 0.3 mL of triethanolamine to the reaction mixture to neutralize the excess hydrochloric acid in the system, and filter to remove the solid salt produced.

[0089] i. Under the conditions of 70℃ and -0.1MPa, the solvent, residual water and excess triethanolamine in the system are removed by vacuum distillation to obtain a zirconium-containing phenyl organosilicon resin prepolymer.

[0090] j. Place the zirconium-containing phenyl silicone resin prepolymer in a vacuum chamber for defoaming. The defoaming temperature is 20℃ and the defoaming time is 10min.

[0091] k. After defoaming, remove it from the vacuum chamber and place it in a muffle furnace for step-by-step curing. The step-by-step curing program is 80℃ x 1h, 100℃ x 1h, 130℃ x 2h, 180℃ x 2h, 220℃ x 2h, and 300℃ x 1h.

[0092] The POSS hybrid zirconium-containing phenyl organosilicon resin obtained in this embodiment passed the inspection, as follows: Figure 1-3 The infrared and XRD spectra shown indicate that POSS was successfully incorporated into the network structure of zirconium-phenyl organosilicon resin via chemical bonds; as shown... Figure 4 The SEM images shown further demonstrate that POSS did not exhibit significant aggregation in the silicone resin, and was uniformly dispersed within the zirconium-phenyl silicone resin. Figure 5-6 The TGA and DTG analyses shown indicate that this silicone resin has excellent thermal stability, with an initial decomposition temperature of 542.1℃, a temperature of 729.7℃ at which 10% decomposition occurs, and a residual weight of up to 88.05% at 800℃.

[0093] Example 2:

[0094] A method for preparing a POSS hybrid zirconium-containing phenyl silicone resin includes the following steps:

[0095] a. Dissolve 3g of n-butanol zirconium hybrid phenyl organosilicon resin prepolymer in 35mL of ethanol to prepare a zirconium-containing phenyl organosilicon resin solution;

[0096] b. Weigh 0.09g of heptaphenyl cage-like polysilsesquioxane trisilol (phenyl T7-POSS) and dissolve it in a zirconium-containing phenyl organosilicon resin solution;

[0097] c. Then add 1 wt% stannous octoate and seal the reactor;

[0098] d. Stir the reaction at 30℃ for 16 hours;

[0099] e. Under the conditions of 70℃ and -0.05MPa, the solvent and residual water in the system are removed by vacuum distillation to obtain POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer.

[0100] f. Place the POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer in a vacuum chamber and allow it to stand for defoaming at 20°C for 10 minutes.

[0101] g. After defoaming, the POSS hybrid zirconium-containing phenyl silicone resin prepolymer is taken out of the vacuum chamber, placed at room temperature for 16 hours, and then cured in an oven at 100°C for 3 hours to obtain the POSS hybrid zirconium-containing phenyl silicone resin.

[0102] The results obtained from the detection of the POSS hybrid zirconium-containing phenyl organosilicon resin in this embodiment are the same as those obtained in Example 1. Figure 1-6 The results are largely consistent, demonstrating that POSS was successfully incorporated into the network structure of the zirconium-phenyl silicone resin via chemical bonds. Furthermore, POSS did not exhibit significant agglomeration within the silicone resin, showing uniform dispersion. TG analysis indicates that the silicone resin possesses excellent thermal stability, with an initial decomposition temperature of 532.7℃, a 10% decomposition temperature of 717.4℃, and a residual weight of 84.28% at 800℃.

[0103] Example 3:

[0104] A method for preparing a POSS hybrid zirconium-containing phenyl silicone resin includes the following steps:

[0105] a. Dissolve 10g of isobutanol zirconium hybrid phenyl organosilicon resin prepolymer in 43mL of methanol to prepare a zirconium-containing phenyl organosilicon resin solution.

[0106] b. Weigh 1g of heptamethyl-T7-POSS cage-like polysilsesquioxane (dimethyl T7-POSS) and dissolve it in a zirconium-phenyl organosilicon resin solution;

[0107] c. Then add 1.5 wt% dibutyltin dilaurate and seal the reactor;

[0108] d. Stir the reaction at 60℃ for 8 hours;

[0109] e. Under conditions of 80℃ and -0.07MPa, the solvent and residual water in the system are removed by vacuum distillation to obtain POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer.

[0110] f. Place the POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer in a vacuum chamber and allow it to stand for defoaming at 20°C for 10 minutes.

[0111] g. After defoaming, the POSS hybrid zirconium-containing phenyl silicone resin prepolymer is taken out of the vacuum chamber, placed at room temperature for 48 hours, and then cured in an oven at 60°C for 7 hours to obtain the POSS hybrid zirconium-containing phenyl silicone resin.

[0112] The results obtained from the detection of the POSS hybrid zirconium-containing phenyl organosilicon resin in this embodiment are the same as those obtained in Example 1. Figure 1-6 The results are largely consistent, demonstrating that POSS was successfully incorporated into the network structure of the zirconium-phenyl silicone resin via chemical bonds. Furthermore, POSS did not exhibit significant agglomeration within the silicone resin, but was uniformly dispersed. TG analysis indicates that the silicone resin possesses excellent thermal stability, with an initial decomposition temperature of 541.0℃, a 10% decomposition temperature of 720.5℃, and a residual weight of up to 84.67% at 800℃.

[0113] Example 4:

[0114] A method for preparing a POSS hybrid zirconium-containing phenyl silicone resin includes the following steps:

[0115] a. Dissolve 5g of isobutanol zirconium hybrid phenyl organosilicon resin prepolymer in 30mL of n-butanol to prepare a zirconium-containing phenyl organosilicon resin solution.

[0116] b. Weigh 0.25g of heptaisobutyl cage-like polysilsesquioxane trisilanol (isobutyl T7-POSS) and dissolve it in a zirconium-phenyl organosilicon resin solution;

[0117] c. Then add 0.1 wt% stannous octoate and seal the reactor;

[0118] d. Stir the reaction at 100℃ for 6 hours;

[0119] e. Under conditions of 90℃ and -0.03MPa, the solvent and residual water in the system are removed by vacuum distillation to obtain POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer.

[0120] f. Place the POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer in a vacuum chamber and allow it to stand for defoaming at 20°C for 10 minutes.

[0121] g. After defoaming, the POSS hybrid zirconium-containing phenyl silicone resin prepolymer is taken out of the vacuum chamber, placed at room temperature for 12 hours, and then cured in an oven at 50°C for 10 hours to obtain the POSS hybrid zirconium-containing phenyl silicone resin.

[0122] The results obtained from the detection of the POSS hybrid zirconium-containing phenyl organosilicon resin in this embodiment are the same as those obtained in Example 1. Figure 1-6 The results are largely consistent, demonstrating that POSS was successfully incorporated into the network structure of the zirconium-phenyl silicone resin via chemical bonds. Furthermore, POSS did not exhibit significant agglomeration within the silicone resin, but was uniformly dispersed. TG analysis indicates that the silicone resin possesses excellent thermal stability, with an initial decomposition temperature of 521.1℃, a 10% decomposition temperature of 698.4℃, and a residual weight of 86.79% at 800℃.

[0123] Example 5:

[0124] A method for preparing a POSS hybrid zirconium-containing phenyl silicone resin includes the following steps:

[0125] a. Dissolve 7g of tert-butanol zirconium hybrid phenyl organosilicon resin prepolymer in 50mL of isopropanol to prepare a zirconium-containing phenyl organosilicon resin solution.

[0126] b. Weigh 0.21g of heptamethyl cage-like polysilsesquioxane (dimethyl T7-POSS) and dissolve it in a zirconium-phenyl organosilicon resin solution;

[0127] c. Then add 2wt% dibutyltin dilaurate and seal the reactor;

[0128] d. Stir the reaction at 10℃ for 24 hours;

[0129] e. Under conditions of 100℃ and -0.01MPa, the solvent and residual water in the system are removed by vacuum distillation to obtain POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer.

[0130] f. Place the POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer in a vacuum chamber and defoam at 20°C for 10 minutes.

[0131] g. After defoaming, the POSS hybrid zirconium-containing phenyl silicone resin prepolymer is taken out of the vacuum chamber and placed at room temperature for 12-48 hours. Then it is cured in an oven at 120°C for 1 hour to obtain the POSS hybrid zirconium-containing phenyl silicone resin.

[0132] The results obtained from the detection of the POSS hybrid zirconium-containing phenyl organosilicon resin in this embodiment are the same as those obtained in Example 1. Figure 1-6The results are largely consistent, demonstrating that POSS was successfully incorporated into the network structure of the zirconium-phenyl silicone resin via chemical bonds. Furthermore, POSS did not exhibit significant agglomeration within the silicone resin, showing uniform dispersion. TG analysis indicates that the silicone resin possesses excellent thermal stability, with an initial decomposition temperature of 537.1℃, a 10% decomposition temperature of 702.3℃, and a residual weight of 87.12% at 800℃.

[0133] Although the above embodiments were carried out under laboratory conditions, the same results will be obtained after scaling up production according to the corresponding scale.

[0134] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or make equivalent substitutions for some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A POSS hybrid zirconium-containing phenyl silicone resin, characterized in that, It is made from components comprising the following mass percentages: Zirconium-containing phenyl silicone resin 90-99% POSS 1-10% The zirconium-containing phenyl organosilicon resin is a zirconium-butanol hybrid phenyl organosilicon resin prepolymer, a zirconium-isobutanol hybrid phenyl organosilicon resin prepolymer, and / or a zirconium-tert-butanol hybrid phenyl organosilicon resin prepolymer; the POSS is a heptaphenyl cage-like polysilsesquioxane trisilol, a heptaisobutyl cage-like polysilsesquioxane trisilol, and / or a heptamethyl cage-like polysilsesquioxane.

2. The method for preparing a POSS hybrid zirconium-containing phenyl silicone resin according to claim 1, characterized in that, The steps involved are as follows: a. Dissolve zirconium-containing phenyl organosilicon resin in a solvent to prepare a zirconium-containing phenyl organosilicon resin solution, wherein the concentration of zirconium-containing phenyl organosilicon resin is 0.02-0.5 g / mL; b. Dissolve POSS in a zirconium-phenyl organosilicon resin solution; c. Add 0.1-2 wt% curing aid and seal the reactor; d. Stir the reaction at 10–100℃ for 6–24 hours; e. Under conditions of 50–100°C and -0.01–0.1 MPa, vacuum distillation was performed to obtain POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer. f. Place the POSS hybrid zirconium-containing phenyl organosilicon resin prepolymer in a vacuum chamber for defoaming; g. Remove it from the vacuum chamber and place it at room temperature for 12-48 hours, then cure it in an oven at 50-120℃ for 1-10 hours.

3. The method for preparing a POSS hybrid zirconium-containing phenyl silicone resin according to claim 2, characterized in that, The solvent is one of ethanol, methanol, n-butanol, isopropanol, or toluene.

4. The method for preparing a POSS hybrid zirconium-containing phenyl silicone resin according to claim 2, characterized in that... The curing aid is one of stannous octoate and dibutyltin dilaurate.

5. The method for preparing a POSS hybrid zirconium-containing phenyl silicone resin according to claim 2, characterized in that, In step f, the defoaming temperature is 20°C and the defoaming time is 10 min.

6. The method for preparing a POSS hybrid zirconium-containing phenyl silicone resin according to claim 2, characterized in that, In step g, the time spent at room temperature is 24 hours, the curing temperature is 80°C, and the curing time is 4 hours.

7. The method for preparing a POSS hybrid zirconium-containing phenyl silicone resin according to claim 2, characterized in that, In step e, the temperature of the vacuum distillation is 50°C, and the pressure of the vacuum distillation is -0.1 MPa.

8. The method for preparing a POSS hybrid zirconium-containing phenyl silicone resin according to claim 2, characterized in that, In step d, the reaction temperature is 70℃ and the reaction time is 12h.

Images