A method for preparing a reactive temperature-resistant hyperbranched organosilicon resin containing chlorohydrocarbon groups

Abstract

The application discloses a preparation method of a reactive temperature-resistant hyperbranched organosilicon resin containing chlorohydrocarbon groups, and belongs to the field of organic polymer chemistry. In the application, the siloxane monomer containing chlorohydrocarbon groups and the siloxane monomer not containing chlorohydrocarbon groups are first hydrolyzed into cores in water, and then the siloxane monomer containing or not containing chlorohydrocarbon groups, water, a solvent and a catalyst are added for condensation growth, and then a capping agent is added for continuous reaction. After the reaction is completed, the solution is subjected to neutralization, filtration and purification treatment, and thus the reactive temperature-resistant hyperbranched organosilicon resin containing chlorohydrocarbon groups is obtained. The preparation method is simple, the proportion of the non-active group and the active group can be regulated according to different application requirements, the method is simple and controllable, and large-scale production can be realized. The obtained organosilicon resin contains two active groups, i.e., reactive hydroxyl groups and hydrocarbon group chlorines, has a highly branched structure, has higher thermal stability and chemical stability, and has the advantages of high functionality, low viscosity, good solubility and low surface free energy.

Description

Technical Field

[0001] This invention belongs to the field of organic polymer chemistry, specifically relating to a method for preparing a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups. Background Technology

[0002] Chloroalkylsiloxanes are a class of monomeric or simple siloxane compounds, organosilicon compounds containing Si-O bonds and at least one chloroalkyl group (such as -CH2Cl / C6H5Cl). They possess multifunctional reactive sites and can undergo substitution, hydrolysis, and condensation reactions, exhibiting milder reactivity compared to chlorosiloxanes (containing Si-Cl bonds). By reacting with hydroxyl groups on material surfaces, reactive chloroalkyl functional groups are introduced, thereby endowing the surface with further chemical reactivity, such as nucleophilic substitution reactions, further graft polymerization, or combination with other organic molecules. However, chloroalkylsiloxanes are monomeric compounds; although they can participate in various chemical reactions and material modification, their heat resistance and thermal stability are relatively poor. In contrast, chloroalkylsiloxanes are condensed to form chloroalkyl organosilicon resins, which have a more complex structure. This retains some of the characteristics of chloroalkylsiloxanes while exhibiting higher mechanical and thermal stability, enabling the material to move from simple monomer applications to a wider and more diverse range of applications, while also bringing higher performance and broader functionality.

[0003] Hyperbranched silicone resins are a novel type of silicone resin with a unique, highly branched three-dimensional network structure, exhibiting higher thermal and chemical stability compared to linear or slightly branched silicone resins. They possess advantages such as high functionality, low viscosity, good solubility, flexible long chains, and low surface free energy. Their most prominent advantage is the designability of their functional groups. Through the hydrolysis and condensation of siloxane monomers, hyperbranched silicone resins can be endowed with various reactive functional groups, such as hydroxyl, amino, amide, and double bonds. Different reactive groups endow hyperbranched silicone resins with diverse properties while maintaining low viscosity. This structural multifunctionality not only provides unprecedented flexibility for hyperbranched silicones but also offers new strategies for addressing increasingly complex technological challenges, demonstrating broad application prospects. For example, Chinese patent CN117050311A discloses a photosensitive hyperbranched silicone resin, its preparation method, and its application. Utilizing the hydrolysis of siloxanes, a hyperbranched silicone resin containing acryloyloxy functional groups is prepared. This resin can be directly used in photocurable additive manufacturing, exhibiting high ceramic formation rate, low shrinkage, and long-term storage. Another example is Chinese patent CN117285850A, which discloses an organic-inorganic hybrid supramolecular epoxy self-lubricating sealing coating and its preparation method. A one-pot method is used to prepare an epoxy hyperbranched polysiloxane with SiOC as the main chain segment. This polysiloxane is then mixed with polyamide solid powder and added to epoxy resin. The addition of the epoxy hyperbranched polysiloxane increases the compatibility between the polyamide solid powder and the epoxy resin, further improving the strength, toughness, and heat resistance of the epoxy resin. This allows it to be applied as a self-lubricating sealing coating for contact sealing components in aerospace and other fields. For example, Chinese patent CN116200033A discloses a halogen-free flame-retardant cyanate ester resin system and its preparation method. This invention utilizes alkylsiloxane, trialkoxy borate, and 4,4'-dihydroxybenzophenone in an organic solvent to prepare boron-containing hyperbranched polysiloxane via transesterification polycondensation. The flame-retardant elements boron and silicon, along with rigid benzene ring groups, are simultaneously introduced into the molecular structure of the hyperbranched polysiloxane. This is then mixed with cyanate ester resin to obtain a flame-retardant cyanate ester resin that combines rigidity and flexibility with excellent performance. Hyperbranched silicone resins have broad application prospects due to their excellent properties, especially the designability of their active functional groups. However, the designable functional groups are far more numerous than those mentioned above, and all have wide applications.

[0004] Currently, there is a lack of relevant articles and patent reports on hyperbranched organosilicon resins containing chlorinated hydrocarbon groups, but they have broad application prospects. The hydroxyl groups produced after resin hydrolysis can react with other active groups, and the chlorinated hydrocarbon group can also undergo many reactions. For example, nucleophilic substitution reactions can be used to chemically introduce hyperbranched organosilicon resins into the resin to form a multi-layered cross-linked network, thereby improving its heat resistance, thermal stability, adhesion, flame retardancy, and moisture resistance. Therefore, providing a method for preparing a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups to improve the application performance of organosilicon resins is of great significance. Summary of the Invention

[0005] To address the aforementioned problems in existing technologies, the present invention aims to provide a reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched organosilicon resin. This chlorinated hydrocarbon-containing hyperbranched organosilicon is a liquid at room temperature and possesses characteristics such as low viscosity, moderate reactivity, and controllable chlorine content, which can be adjusted according to application requirements. Another objective of the present invention is to provide a method for preparing this reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched organosilicon resin. This method allows for quantitative control according to different application requirements, and the preparation method is simple, controllable, and suitable for large-scale production.

[0006] To solve the above problems, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups involves using chlorinated hydrocarbon-containing siloxane monomers and non-chlorinated hydrocarbon-containing siloxane monomers as raw materials, mixing them with water and reacting them, then adding siloxane monomers, water, solvents, and catalysts to react and obtain a solution. An end-capping agent is then added to cap the solution, and the reacted solution is purified to obtain the reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups.

[0008] Furthermore, the chlorinated hydrocarbon-containing siloxane monomer is selected from one or more of chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, chloromethylmethyldimethoxysilane, chloromethylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 4-(chloromethyl)phenyltrimethoxysilane, 4-(chloromethyl)phenyltriethoxysilane, p-chlorophenyltrimethoxysilane, and p-chlorophenyltriethoxysilane.

[0009] Furthermore, the non-chlorinated hydrocarbon siloxane monomer is selected from one or more of dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

[0010] Furthermore, the molar ratio of chlorinated hydrocarbon-based siloxane monomers to non-chlorinated hydrocarbon-based siloxane monomers is 0.01–0.99:0.99–0.01, and the molar ratio of siloxane monomers to water is 1:0.5–3.

[0011] Furthermore, the reaction temperature is 0–150℃; the reaction time is 1–36 h.

[0012] Further, the solvent is selected from one or more of tetrahydrofuran, acetone, dichloromethane, ethyl acetate, toluene, methanol, ethanol, N-methylpyrrolidone, and N,N-dimethylformamide; the catalyst is selected from one or more of sulfuric acid, phosphoric acid, hydrochloric acid, benzoic acid, benzenesulfonic acid, ammonium chloride, sodium hydroxide, triethylamine, ammonia, and tetramethylammonium hydroxide; the solvent content is 20% to 90%, and the catalyst addition amount is 0.1% to 5% of the total mass of the siloxane monomer.

[0013] Furthermore, the end-capping agent is selected from one or more of 1,3-bis(chloromethyl)tetramethyldisiloxane, chloromethylpentamethyldisiloxane, 1,3-bis(3-chloropropyl)tetramethyldisiloxane, hexamethyldisiloxane, and hexaphenyldisiloxane.

[0014] Furthermore, the preparation method of any of the above-mentioned reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched organosilicon resins comprises the following steps:

[0015] (1) Mix siloxane monomers containing chlorinated hydrocarbon groups, siloxane monomers without chlorinated hydrocarbon groups and water, react at a temperature of 0 to 150°C, react for 1 to 24 hours, the molar ratio of siloxane monomers containing chlorinated hydrocarbon groups to siloxane monomers without chlorinated hydrocarbon groups is 0.01 to 0.99: 0.99 to 0.01, and the molar ratio of siloxane monomers to water is 1: 0.5 to 3;

[0016] (2) Continue to add siloxane monomers containing chlorinated hydrocarbon groups or siloxane monomers without chlorinated hydrocarbon groups, water, solvent and catalyst; wherein, the molar ratio of siloxane monomers to water is 1:0.5-2, the solvent content is 20%-90%, the amount of catalyst added is 0.1%-5% of the total mass of siloxane monomers, the reaction temperature is 0-150℃, the reaction time is 1-36h, and the molar ratio of siloxane monomers containing chlorinated hydrocarbon groups to siloxane monomers without chlorinated hydrocarbon groups is 0.01-0.99:0.99-0.01;

[0017] (3) Add the end-capping agent to the solution after condensation growth in step (2) and continue the reaction. The molar ratio of the end-capping agent to the siloxane monomer is 1:2 to 10, the reaction temperature is 0 to 150°C, the reaction time is 1 to 12 h, and the solution is neutralized and filtered after the reaction is completed.

[0018] (4) The solution after the reaction in step (3) is purified to obtain a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups.

[0019] Furthermore, any of the methods described above can be used to prepare a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups.

[0020] Furthermore, the aforementioned reactive, heat-resistant, chlorinated hydrocarbon-based hyperbranched silicone resin is used in the preparation and modification of silicone polymers, special polymers, and composite materials in the fields of aerospace, electronic packaging, and transportation.

[0021] Compared with the prior art, the advantages of the present invention are as follows:

[0022] 1) The chlorinated hydrocarbon-based hyperbranched organosilicon resin prepared by this invention is a further polymerization or crosslinking product based on chlorinated hydrocarbon-based siloxane monomers. This resin not only inherits the characteristics of the monomers, but also forms a more complex and stable macromolecular network structure, which gives these resins a higher crosslinking density and improves their mechanical strength and thermal stability.

[0023] 2) This invention is formed by the co-hydrolysis and condensation of hydrocarbon-based siloxanes and chlorinated hydrocarbon-based siloxanes, resulting in a unique hyperbranched structure. While having a high chlorine content, the resin has low viscosity, overcoming the limitations of high viscosity and poor compatibility in existing organosilicon resin technology. At the same time, the introduced reactive chlorinated hydrocarbon functional groups have further chemical reactivity capabilities, such as further graft polymerization or combination with other organic molecules, thereby introducing siloxane segments into organic matter to form a resin with stronger binding ability and better compatibility. This further improves the resin's heat resistance, thermal stability, adhesion, and moisture resistance. Moreover, the ratio of inactive and active groups can be flexibly controlled, allowing for quantitative control according to different application requirements. The preparation method is simple and controllable, and can be mass-produced. Attached Figure Description

[0024] Figure 1 This diagram illustrates the preparation process of the reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched silicone resin of this invention.

[0025] Figure 2 This is a physical image of a reactive, heat-resistant, hyperbranched silicone resin containing chlorinated hydrocarbon groups.

[0026] Figure 3 The infrared spectrum of the reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched silicone resin in Example 1 is shown.

[0027] Figure 4 The thermogravimetric curves of the reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched silicone resin in Example 1 are shown.

[0028] Figure 5 XPS curves of the reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched silicone resin in Example 1.

[0029] Figure 6 The image shows a comparison of the reactive, heat-resistant, chlorinated hydrocarbon-based hyperbranched silicone resin before and after ablation in Example 1. Detailed Implementation

[0030] To make the above-mentioned objectives, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to specific examples.

[0031] Unless otherwise specified, all raw materials or reagents used in the following examples are commercially available products.

[0032] A method for preparing a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups, such as... Figure 1 As shown, the steps are as follows:

[0033] (1) Nucleation: Mix siloxane monomers containing chlorinated hydrocarbon groups, non-chlorinated hydrocarbon groups and water. The reaction temperature is 0-150℃ and the reaction time is 1-24h. The molar ratio of siloxane monomers containing chlorinated hydrocarbon groups to non-chlorinated hydrocarbon groups is 0.01-0.99:0.99-0.01. The molar ratio of siloxane monomers to water is 1:0.5-3.

[0034] (2) Growth: After hydrolysis and nucleation, siloxane monomers containing chlorinated hydrocarbon groups or non-chlorinated hydrocarbon groups, water, solvent and catalyst are added; wherein, the molar ratio of siloxane monomer to water is 1:0.5-2, the solvent content is 20%-90%, the amount of catalyst added is 0.1%-5% of the total mass of siloxane monomer, the reaction temperature is 0-150℃, the reaction time is 1-36h, and the molar ratio of siloxane monomers containing chlorinated hydrocarbon groups to non-chlorinated hydrocarbon groups is 0.01-0.99:0.99-0.01;

[0035] (3) End capping: The end capping agent is added to the solution after condensation growth in step (2) and the reaction continues. The molar ratio of the end capping agent to the siloxane monomer is 1:2 to 10, the reaction temperature is 0 to 150°C, the reaction time is 1 to 12 hours, and the solution is neutralized and filtered after the reaction is completed.

[0036] (4) Purification: The solution after the reaction in step (3) is purified to obtain a reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched organosilicon resin.

[0037] Example 1

[0038] A method for preparing a reactive, heat-resistant, chlorinated hydrocarbon-based hyperbranched organosilicon resin, comprising the following steps:

[0039] (1) Nucleation: 27.24 g of methyltrimethoxysilane, 8.53 g of chloromethyltrimethoxysilane and 3.6 g of deionized water were added to a three-necked flask equipped with a stirrer and a reflux condenser, and the mixture was reacted at room temperature for 4 h.

[0040] (2) Growth: Then add 8.53g chloromethyltriethoxysilane, 0.45g deionized water, 10mL tetrahydrofuran and 0.825mL HCl (36.5wt.%), and react at 70℃ for 6h.

[0041] (3) End capping: Add 1.715g of hexamethyldisiloxane to (2) and continue the reaction for 3h.

[0042] (4) Purification: After the reaction is complete, the resin solution is removed by rotary evaporation to remove the solvent and small molecule monomers, resulting in a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups, denoted as Resin 1. Figure 2 As shown.

[0043] The reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched silicone resin (resin 1) obtained in this embodiment was subjected to infrared spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy analysis; the results are as follows: Infrared spectrum as shown in Figure 1. Figure 3 As shown; thermogravimetric curves are as follows Figure 4 As shown; XPS curve as Figure 5 As shown. Additionally, a comparison was made before and after ablation of the reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched silicone resin (resin 1), and the results are as follows. Figure 6 As shown.

[0044] Example 2

[0045] A method for preparing a reactive, heat-resistant, chlorinated hydrocarbon-based hyperbranched organosilicon resin, comprising the following steps:

[0046] (1) Nucleation: 7.41 g of dimethyldiethoxysilane, 8.74 g of methyltriethoxysilane and 0.89 g of distilled water were added to a three-necked flask equipped with a stirrer and a reflux condenser, and the mixture was reacted at 150 °C for 1 h.

[0047] (2) Growth: Then add 0.99g chloropropyltrimethoxysilane, 1.20g chloropropyltriethoxysilane, 0.09g distilled water, 20mL N-methylpyrrolidone and 1.25mL, 0.1mol / L NaOH, and react at 150℃ for 1h.

[0048] (3) End-capping: Add 1.514g of hexamethyldisiloxane to (2) and continue the reaction for 1h. After the reaction is completed, add a small amount of hydrochloric acid to adjust the pH to 7 and neutralize the solution.

[0049] (4) Purification: After the reaction is complete, the resin solution is vacuum-dried in a vacuum oven to remove the solvent and small molecule monomers, yielding a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups, denoted as Resin 2. Figure 2 As shown.

[0050] Example 3

[0051] A method for preparing a reactive, heat-resistant, chlorinated hydrocarbon-based hyperbranched organosilicon resin, comprising the following steps:

[0052] (1) Nucleation: Add 0.40g phenyltrimethoxysilane, 0.36g methylphenyldimethoxysilane and 0.216g deionized water to a three-necked flask equipped with a stirrer and a reflux condenser, and react at 0℃ for 24h.

[0053] (2) Growth: Then add 92.16g of p-chlorophenyltrimethoxysilane, 7.2g of deionized water, 100mL of dichloromethane and 2.3mL of HCl (36.5wt.%), and react at 0℃ for 36h.

[0054] (3) End-capping: Add 15.24g of hexaphenyldisiloxane to (2) and continue the reaction for 6h.

[0055] (4) Purification: After the reaction is complete, the resin solution is subjected to vacuum distillation to remove the solvent and small molecule monomers, yielding a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups, denoted as Resin 3. Figure 2 As shown.

[0056] Example 4

[0057] A method for preparing a reactive, heat-resistant, chlorinated hydrocarbon-based hyperbranched organosilicon resin, comprising the following steps:

[0058] (1) Nucleation: Add 12.02g of phenyltriethoxysilane and 0.9g of deionized water to a three-necked flask equipped with a stirrer and a reflux condenser, and react at 70°C for 6h.

[0059] (2) Growth: Then add 1.83g 3-chloropropylmethyldimethoxysilane, 0.36g deionized water, 50mL acetone and 1.6g benzenesulfonic acid, and react at 110℃ for 2h.

[0060] (3) End capping: Add 1.24g of chloromethylpentamethyldisiloxane to (2) and continue the reaction for 5h.

[0061] (4) Purification: After the reaction is complete, the resin solution is removed by rotary evaporation to remove the solvent and small molecule monomers, and then filtered to obtain a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups, denoted as Resin 4. Figure 2 As shown.

[0062] Example 5

[0063] A method for preparing a reactive, heat-resistant, chlorinated hydrocarbon-based hyperbranched organosilicon resin, comprising the following steps:

[0064] (1) Nucleation: 142.3g of diphenyldimethoxysilane, 68.4g of vinyltrimethoxysilane, 175.6g of chloromethyltrimethoxysilane and 21.3g of purified water were added to a three-necked flask equipped with a stirrer and a reflux condenser, and the mixture was reacted at room temperature for 3 hours.

[0065] (2) Growth: Then add 92.8g of 4-(chloromethyl)phenyltrimethoxysilane, 42.4g of purified water, 485mL of ethyl acetate and 12.5mL of HCl (36.5wt.%), and react at 70℃ for 2h.

[0066] (3) End capping: Add 31.6g of chloromethylpentamethyldisiloxane to (2) and continue the reaction for 5h.

[0067] (4) Purification: After the reaction is complete, the resin solution is subjected to vacuum distillation to remove the solvent and small molecule monomers, yielding a hyperbranched organosilicon resin containing chlorinated hydrocarbon groups, denoted as resin 5. Figure 2 As shown.

[0068] The reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched silicone resins prepared in Examples 1-5 above are shown in the figure. Figure 2 As shown.

[0069] Comparative Example 1

[0070] The preparation method of terminal alkoxy polysiloxane is as follows: In a high-speed disperser, dihydroxy polydimethylsiloxane, vinyltrimethoxysilane, methyltriethoxysilane, N-cyclohexyl-γ-aminopropyltrimethoxysilane, piperidinylpropyltriethoxysilane, and piperazineylpropyltriethoxysilane are added to the high-speed disperser. Under inert gas, the mixture is stirred at 800 r / min for 15 min. The uniformly stirred mixture is then placed at 25°C for 6 h under inert gas to carry out in-situ terminal alkylation and end-capping reaction, resulting in a terminal alkoxy polysiloxane with a viscosity of 47700 mPa·s.

[0071] Comparative Example 2

[0072] A phenyl silicone resin and its preparation method are disclosed, comprising the following steps: hydroxyl-terminated methyltrifluoropropylsiloxane is dissolved in toluene, and then added dropwise to a flask containing a mixture of dimethyldichlorosilane, toluene, and diethylamine. Under nitrogen protection, the mixture is stirred at 25°C for 1 hour. After the reaction is complete, the tail gas HCl is absorbed with a 1 mol / L sodium hydroxide aqueous solution to obtain the product. The entire product is added dropwise to a mixture containing phenyl silicone resin prepolymer and diethylamine, stirred at 10°C for 1 hour, filtered, and then 100 parts of distilled water are added at 10°C. The mixture is stirred for 30 minutes and dried to obtain the phenyl silicone resin.

[0073] The viscosity of the silicone resins obtained in Examples 1-5 and Comparative Examples 1-2 was tested according to GB / T10247-2008. The test results are shown in Table 1 below.

[0074] Table 1. Viscosity, chlorine content, and T of the organosilicon resins obtained in Examples 1-5 and Comparative Examples 1-2 of this invention. d10％ Comparison Table

[0075] Resin viscosity (mPa·s) Chlorine content (wt%) <![CDATA[T d10％ (℃)]]> Example 1 389 5.38 326 Example 2 304 0.59 351 Example 3 219 13.21 371 Example 4 234 2.37 337 Example 5 287 5.05 301 Comparative Example 1 47700 / / Comparative Example 2 3000 / /

[0076] As can be seen from the data in Table 1, compared with Comparative Example 1 and Comparative Example 2, Comparative Example 1, which is a polysiloxane with terminal alkoxy groups synthesized by reacting hydroxyl polysiloxane with other siloxane monomers, has a relatively high overall viscosity, poor flowability, and a simpler reaction, although it contains hydroxyl and alkoxy reactive groups. Comparative Example 2 is a high molecular weight heat-resistant phenyl silicone resin (resistant to 300℃) obtained by reacting hydroxyl-terminated siloxane monomers with chlorosilane monomers and water to release HCl, and then mixing it with phenyl silicone resin prepolymer. Although the obtained phenyl silicone resin has excellent heat resistance, the reaction between Si-Cl and active hydrogen is violent, and the prepared silicone resin contains almost no Cl, resulting in a reduction of its reactive groups. At the same time, the high viscosity of phenyl silicone resin makes it difficult to be compatible with other high-performance polymer materials. It can only be added in small amounts through physical blending, which greatly reduces its application scenarios.

[0077] The reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched silicone resin obtained by this invention not only has low viscosity and good temperature resistance, providing a basis for further addition of other functional fillers; but also contains reactive hydroxyl and hydrocarbon chlorine groups, which can be introduced into the resin through a nucleophilic substitution reaction to form a multi-linked network, thereby improving its heat resistance, thermal stability, adhesion, flame retardancy, and moisture resistance, etc., and its content can be flexibly controlled within a wide range, making it suitable for various different systems.

[0078] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups, characterized in that, Using chlorinated hydrocarbon-containing siloxane monomers and non-chlorinated hydrocarbon-containing siloxane monomers as raw materials, water is added and the mixture is reacted. Then, siloxane monomers, water, solvent, and catalyst are added to react and obtain a solution. An end-capping agent is then added to cap the solution. The resulting solution is purified to obtain a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups. The steps are as follows: (1) Mix siloxane monomers containing chlorinated hydrocarbon groups, siloxane monomers without chlorinated hydrocarbon groups and water. The reaction temperature is 0~150 ℃ and the reaction time is 1~24 h. The molar ratio of siloxane monomers containing chlorinated hydrocarbon groups to siloxane monomers without chlorinated hydrocarbon groups is 0.01~0.99:0.99~0.01, and the molar ratio of siloxane monomers to water is 1:0.5~3. (2) Continue to add siloxane monomers containing chlorinated hydrocarbon groups or siloxane monomers without chlorinated hydrocarbon groups, water, solvent and catalyst; wherein, the molar ratio of siloxane monomers to water is 1:0.5~2, the solvent content is 20%~90%, the amount of catalyst added is 0.1%~5% of the total mass of siloxane monomers, the reaction temperature is 0~150 ℃, the reaction time is 1~36 h, and the molar ratio of siloxane monomers containing chlorinated hydrocarbon groups to siloxane monomers without chlorinated hydrocarbon groups is 0.01~0.99:0.99~0.01; (3) Add the end-capping agent to the solution after condensation growth in step (2) and continue the reaction. The molar ratio of the end-capping agent to the siloxane monomer is 1:2~10, the reaction temperature is 0~150 ℃, the reaction time is 1~12 h, and the solution is neutralized and filtered after the reaction is completed. (4) Purify the solution after the reaction in step (3) to obtain a reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups.

2. The method for preparing the reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched organosilicon resin according to claim 1, characterized in that, The chlorinated hydrocarbon-containing siloxane monomer is selected from one or more of chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, chloromethylmethyldimethoxysilane, chloromethylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 4-(chloromethyl)phenyltrimethoxysilane, 4-(chloromethyl)phenyltriethoxysilane, p-chlorophenyltrimethoxysilane, and p-chlorophenyltriethoxysilane.

3. The method for preparing the reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched organosilicon resin according to claim 1, characterized in that, The non-chlorinated hydrocarbon siloxane monomer is selected from one or more of dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

4. The method for preparing the reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched organosilicon resin according to claim 1, characterized in that, The solvent is selected from one or more of tetrahydrofuran, acetone, dichloromethane, ethyl acetate, toluene, methanol, ethanol, N-methylpyrrolidone, and N,N-dimethylformamide; the catalyst is selected from one or more of sulfuric acid, phosphoric acid, hydrochloric acid, benzoic acid, benzenesulfonic acid, ammonium chloride, sodium hydroxide, triethylamine, ammonia, and tetramethylammonium hydroxide; the solvent content is 20% to 90%, and the catalyst addition amount is 0.1% to 5% of the total mass of the siloxane monomer.

5. The method for preparing the reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched organosilicon resin according to claim 1, characterized in that, The end-capping agent is selected from one or more of 1,3-bis(chloromethyl)tetramethyldisiloxane, chloromethylpentamethyldisiloxane, 1,3-bis(3-chloropropyl)tetramethyldisiloxane, hexamethyldisiloxane, and hexaphenyldisiloxane.

6. A reactive, heat-resistant, hyperbranched organosilicon resin containing chlorinated hydrocarbon groups prepared by the method according to any one of claims 1 to 5.

7. The application of the reactive, heat-resistant, chlorinated hydrocarbon-based hyperbranched organosilicon resin according to claim 6 in the preparation and modification of organosilicon polymers, special polymers, and composite materials in the fields of aerospace, electronic packaging, and transportation.

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