CN118878826A - A method for preparing a reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups - Google Patents

Abstract

The invention discloses a method for preparing a reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbon groups, and belongs to the field of organic polymer chemistry. The invention first hydrolyzes siloxane monomers containing chlorinated hydrocarbon groups and siloxane monomers containing non-chlorinated hydrocarbon groups in water to form nuclei, adds siloxane monomers containing or not containing chlorinated hydrocarbon groups, water, solvents and catalysts for condensation growth, then adds a capping agent to continue the reaction, and after the reaction is completed, the solution is neutralized, filtered and purified to obtain a reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbon groups. The preparation method of the invention is simple and can adjust the ratio of inactive groups and active groups according to different application requirements, is simple and controllable, and can achieve large-scale production; the obtained organosilicon resin contains two reactive groups, namely, hydroxyl groups and hydrocarbon chlorides, and has a highly branched structure, higher thermal stability and chemical stability, and has the advantages of high functionality, low viscosity, good solubility and low surface free energy.

Description

A method for preparing a reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups

Technical Field

The invention belongs to the field of organic polymer chemistry, and in particular relates to a method for preparing a reactive temperature-resistant hyperbranched organic silicon resin containing chlorinated hydrocarbon groups.

Background Art

Chloroalkylsiloxanes are a class of monomers or simple siloxane compounds, which are organic silicon compounds containing Si-O bonds and at least one chloroalkyl group (such as -CH ₂ Cl/C ₆ H ₅ Cl). They have multifunctional reactive sites and can undergo substitution, hydrolysis, and condensation reactions. Compared with chlorosiloxanes (containing Si-Cl bonds), they have milder reactivity. By reacting with the hydroxyl groups on the surface of the material, reactive chloroalkyl functional groups are introduced, thereby making the surface capable of further chemical reactions, such as nucleophilic substitution reactions, further grafting polymerization, or combination with other organic molecules. However, chloroalkylsiloxanes are monomeric compounds. Although they can participate in a variety of chemical reactions and material modifications, they have poor heat resistance and thermal stability. In contrast, chloroalkyl silicone resins made from chloroalkyl siloxanes through condensation have a more complex structure, retaining some of the characteristics of chloroalkyl siloxanes while exhibiting higher mechanical and thermal stability, allowing the material to move from simple monomer applications to a wider and more diverse range of applications, while bringing higher performance and broader functionality.

Hyperbranched silicone resin is a new type of silicone resin with a unique highly branched three-dimensional network structure. Compared with linear or slightly branched silicone resins, it has higher thermal stability and chemical stability. It has the advantages of high functionality, low viscosity, good solubility, flexible chain length and low surface free energy. The most prominent advantage is the designability of its functional groups. Through the hydrolysis and condensation of siloxane monomers, hyperbranched silicone resins can be endowed with a variety of reactive functional groups, such as hydroxyl, amino, amide, double bonds, etc. Different reactive groups give hyperbranched silicone resins a variety of properties while maintaining the characteristics of low viscosity. This structural versatility not only provides unprecedented flexibility for hyperbranched silicone, but also provides new strategies for coping with increasingly complex technical challenges, and has broad application prospects. For example, Chinese patent CN117050311A discloses a photosensitive hyperbranched silicone resin and its preparation method and application. By hydrolyzing siloxane, a hyperbranched silicone resin containing acryloxy functional groups is prepared, which can be directly used for photocuring additive molding, has a high ceramic ceramic rate, low shrinkage rate, and can be stored for a long time. For another example, Chinese patent CN117285850A discloses an organic-inorganic hybrid supramolecular epoxy self-lubricating sealing coating and a preparation method. An epoxy hyperbranched polysiloxane with a main chain segment of SiOC is prepared by a one-pot method, and it is mixed with polyamide solid powder and added to epoxy resin. The addition of epoxy hyperbranched polysiloxane is conducive to increasing the compatibility of polyamide solid powder with epoxy resin, and further improving the strength, toughness and heat resistance of epoxy resin. It can be applied to self-lubricating sealing coatings of contact sealing parts in the fields of aviation and aerospace. Another example is the Chinese patent CN116200033A, which discloses a halogen-free flame-retardant cyanate resin system and preparation method. The invention uses alkyl siloxane, trialkyloxy borate and 4,4' dihydroxybenzophenone in an organic solvent through an ester exchange polycondensation method to prepare a boron-containing hyperbranched polysiloxane, introduces flame-retardant elements boron, silicon and rigid benzene ring groups into the molecular structure of the hyperbranched polysiloxane at the same time, and mixes it with a cyanate resin to obtain a rigid and flexible flame-retardant cyanate resin with excellent performance. Hyperbranched silicone resins have broad application prospects due to their excellent performance, especially the designability of active functional groups. However, their designable functional groups are far more than that, and they all have a wide range of uses.

At present, there is still no information about hyperbranched silicone resin containing chlorinated hydrocarbon groups in relevant articles and patent reports, but it has broad application prospects. The hydroxyl groups generated by the hydrolysis of the resin can react with other active groups, and the hydrocarbon chloride group can also undergo many reactions, such as using nucleophilic substitution reactions to introduce hyperbranched silicone resins into the resin through chemical reactions to form multiple cross-linked networks, thereby improving its heat resistance, thermal stability, adhesion, flame retardancy and moisture resistance. Therefore, how to provide a method for preparing a reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups, thereby improving the application performance of silicone resins, is of great significance.

Summary of the invention

In view of the above problems existing in the prior art, the object of the present invention is to provide a reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbon groups, which is a liquid at room temperature, has low viscosity, moderate reactivity, and controllable chlorine content, and can be regulated according to use requirements. Another object of the present invention is to provide a method for preparing a reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbon groups, which can be quantitatively regulated according to different application requirements, and the preparation method is simple and controllable, and can be mass-produced.

In order to solve the above problems, the technical solution adopted by the present invention is as follows:

A method for preparing a reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbon groups comprises the following steps: using a siloxane monomer containing chlorinated hydrocarbon groups and a siloxane monomer containing non-chlorinated hydrocarbon groups as raw materials, adding water for mixed reaction, then adding the siloxane monomer, water, a solvent and a catalyst for reaction to obtain a solution, then adding a capping agent for end-capping, and purifying the solution after the reaction to obtain the reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbon groups.

Further, the siloxane monomer containing a chlorinated hydrocarbon group 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.

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-glycidyloxypropyltrimethoxysilane.

Furthermore, the molar ratio of the siloxane monomer containing a chlorinated hydrocarbon group to the siloxane monomer containing a non-chlorinated hydrocarbon group is 0.01-0.99:0.99-0.01, and the molar ratio of the siloxane monomer to water is 1:0.5-3.

Furthermore, the reaction temperature is 0 to 150° C.; and the reaction time is 1 to 36 hours.

Furthermore, 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 water, 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.

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.

Furthermore, the preparation method of any of the above-mentioned reactive heat-resistant hyperbranched silicone resins containing chlorinated hydrocarbon groups comprises the following steps:

(1) mixing a siloxane monomer containing a chlorinated hydrocarbon group, a siloxane monomer containing a non-chlorinated hydrocarbon group and water, the reaction temperature being 0 to 150° C., the reaction time being 1 to 24 hours, the molar ratio of the siloxane monomer containing a chlorinated hydrocarbon group to the siloxane monomer containing a non-chlorinated hydrocarbon group being 0.01 to 0.99:0.99 to 0.01, and the molar ratio of the siloxane monomer to water being 1:0.5 to 3;

(2) continuing to add siloxane monomers containing chlorinated hydrocarbon groups or siloxane monomers containing non-chlorinated hydrocarbon groups, water, solvents and catalysts; 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 the siloxane monomers, the reaction temperature is 0-150° C., the reaction time is 1-36 hours, and the molar ratio of siloxane monomers containing chlorinated hydrocarbon groups to siloxane monomers containing non-chlorinated hydrocarbon groups is 0.01-0.99:0.99-0.01;

(3) adding a capping agent to the solution after condensation growth in step (2) to continue the reaction, wherein the molar ratio of the 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 after the reaction is completed, the solution is neutralized and filtered;

(4) Purifying the solution after the reaction in step (3) to obtain a reactive temperature-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups.

Furthermore, any of the above methods can prepare a reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched silicone resin.

Furthermore, the reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups is used in the preparation and modification of silicone polymers, special high molecular polymers and composite materials involved in the fields of aerospace, electronic packaging and transportation.

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

1) The chlorinated hydrocarbon group-containing hyperbranched organosilicon resin prepared by the present invention is a further polymerization or cross-linking product based on chlorinated hydrocarbon siloxane monomers. This resin not only inherits the properties of the monomer, but also forms a more complex and more stable macromolecular network structure, so that these resins have a higher cross-linking density, and their mechanical strength and thermal stability are improved.

2) The present invention is prepared by co-hydrolysis and condensation of a hydrocarbon siloxane and a siloxane containing a chlorinated hydrocarbon group, thereby forming a unique hyperbranched structure. The resin has a high chlorine content and low viscosity, thus getting rid of the high viscosity and poor compatibility limitations of the existing silicone resin technology. At the same time, the introduced reactive chlorinated hydrocarbon functional groups have further chemical reaction capabilities, such as further graft polymerization or combination with other organic molecules, thereby introducing the siloxane chain segments into organic matter to form a resin with stronger binding ability and better compatibility, further improving the heat resistance, thermal stability, adhesion and moisture resistance of the resin, and the ratio of the inactive group to the active group can be flexibly controlled, and can be quantitatively controlled according to different application requirements. The preparation method is simple and controllable, and can be mass-produced.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing the preparation process of the reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups according to the present invention.

FIG. 2 is a physical picture of a reactive, heat-resistant, chlorinated hydrocarbon-containing hyperbranched silicone resin.

FIG3 is an infrared spectrum of the reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups in Example 1.

FIG. 4 is a thermogravimetric curve of the reactive temperature-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups in Example 1.

FIG. 5 is an XPS curve of the reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups in Example 1.

FIG6 is a comparison diagram of the reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups in Example 1 before and after ablation.

DETAILED DESCRIPTION

In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with specific embodiments.

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

A method for preparing a reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups, as shown in FIG1 , comprises the following steps:

(1) Nucleation: mixing a siloxane monomer containing a chlorinated hydrocarbon group, a siloxane monomer containing a non-chlorinated hydrocarbon group and water, the reaction temperature being 0 to 150° C., the reaction time being 1 to 24 hours, the molar ratio of the siloxane monomer containing a chlorinated hydrocarbon group to the siloxane monomer containing a non-chlorinated hydrocarbon group being 0.01 to 0.99:0.99 to 0.01, and the molar ratio of the siloxane monomer to water being 1:0.5 to 3;

(2) Growth: After hydrolysis to form nuclei, continue to add siloxane monomers containing chlorinated hydrocarbon groups or siloxane monomers containing non-chlorinated hydrocarbon groups, water, solvents and catalysts; 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 the siloxane monomers, the reaction temperature is 0-150° C., the reaction time is 1-36 hours, and the molar ratio of siloxane monomers containing chlorinated hydrocarbon groups to siloxane monomers containing non-chlorinated hydrocarbon groups is 0.01-0.99:0.99-0.01;

(3) Capping: adding a capping agent to the solution after condensation growth in step (2) to continue the reaction, the molar ratio of the capping agent to the siloxane monomer is 1:2-10, the reaction temperature is 0-150°C, the reaction time is 1-12h, and after the reaction is completed, the solution is neutralized and filtered;

(4) Purification: Purify the solution after the reaction in step (3) to obtain a reactive temperature-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups.

Example 1

A method for preparing a reactive heat-resistant chlorinated hydrocarbon-containing hyperbranched silicone resin comprises the following steps:

(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 stirring and condensation reflux device, and the mixture was reacted at room temperature for 4 h.

(2) Growth: 8.53 g of chloromethyltriethoxysilane, 0.45 g of deionized water, 10 mL of tetrahydrofuran and 0.825 mL of HCl (36.5 wt.%) were then added and reacted at 70° C. for 6 h.

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

(4) Purification: After the reaction is completed, the resin solution is subjected to rotary evaporation to remove the solvent and small molecular monomers to obtain a reactive temperature-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups, which is denoted as resin 1, as shown in FIG. 2 .

The reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbon groups (resin 1) obtained in this example was subjected to infrared spectrum analysis, thermogravimetric analysis and X-ray photoelectron spectroscopy analysis respectively; the results were as follows: the infrared spectrum is shown in FIG3 ; the thermogravimetric curve is shown in FIG4 ; and the XPS curve is shown in FIG5 . In addition, the reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbon groups (resin 1) was compared before and after ablation, and the results were shown in FIG6 .

Example 2

A method for preparing a reactive heat-resistant chlorinated hydrocarbon-containing hyperbranched silicone resin comprises the following steps:

(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 stirring and condensation reflux device, and the mixture was reacted at 150° C. for 1 h.

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

(3) End-capping: 1.514 g of hexamethyldisiloxane was added to (2) and the reaction was continued for 1 h. After the reaction was completed, a small amount of hydrochloric acid was added to adjust the pH to 7 to neutralize the solution.

(4) Purification: After the reaction is completed, the resin solution is passed through a vacuum oven to remove the solvent and small molecular monomers, thereby obtaining a reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups, which is referred to as resin 2, as shown in FIG. 2 .

Example 3

A method for preparing a reactive heat-resistant chlorinated hydrocarbon-containing hyperbranched silicone resin comprises the following steps:

(1) Nucleation: In a three-necked flask equipped with a stirring and condensation reflux device, 0.40 g of phenyltrimethoxysilane, 0.36 g of methylphenyldimethoxysilane and 0.216 g of deionized water were added and reacted at 0°C for 24 h.

(2) Growth: Then, 92.16 g of p-chlorophenyltrimethoxysilane, 7.2 g of deionized water, 100 mL of dichloromethane and 2.3 mL of HCl (36.5 wt.%) were added and reacted at 0°C for 36 h.

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

(4) Purification: After the reaction is completed, the resin solution is subjected to reduced pressure distillation to remove the solvent and small molecular monomers to obtain a reactive temperature-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups, which is denoted as resin 3, as shown in FIG. 2 .

Example 4

A method for preparing a reactive heat-resistant chlorinated hydrocarbon-containing hyperbranched silicone resin comprises the following steps:

(1) Nucleation: 12.02 g of phenyltriethoxysilane and 0.9 g of deionized water were added to a three-necked flask equipped with a stirring and condensation reflux device, and the mixture was reacted at 70° C. for 6 h.

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

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

(4) Purification: After the reaction is completed, the resin solution is subjected to rotary evaporation to remove the solvent and small molecular monomers, and filtered to obtain a reactive temperature-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups, which is referred to as resin 4, as shown in FIG. 2 .

Example 5

A method for preparing a reactive heat-resistant chlorinated hydrocarbon-containing hyperbranched silicone resin comprises the following steps:

(1) Nucleation: 142.3 g of diphenyldimethoxysilane, 68.4 g of vinyltrimethoxysilane, 175.6 g of chloromethyltrimethoxysilane and 21.3 g of pure water were added to a three-necked flask equipped with a stirring and condensation reflux device, and the reaction was carried out at room temperature for 3 h.

(2) Growth: Then, 92.8 g of 4-(chloromethyl)phenyltrimethoxysilane, 42.4 g of purified water, 485 mL of ethyl acetate and 12.5 mL of HCl (36.5 wt.%) were added and reacted at 70° C. for 2 h.

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

(4) Purification: After the reaction is completed, the resin solution is subjected to reduced pressure distillation to remove the solvent and small molecular monomers to obtain a hyperbranched silicone resin containing chlorinated hydrocarbon groups, which is denoted as resin 5, as shown in FIG. 2 .

The actual product of the reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups prepared in the above Examples 1 to 5 is shown in FIG. 2 .

Comparative Example 1

The preparation method of terminal alkoxy polysiloxane comprises the following steps: adding dihydroxy polydimethylsiloxane, vinyl trimethoxysilane, methyl triethoxysilane, N-cyclohexyl-γ-aminopropyl trimethoxysilane, piperidinyl propyl triethoxysilane and piperazinyl propyl triethoxysilane into a high-speed disperser, stirring at a high speed of 800 r/min for 15 minutes under an inert gas, placing the uniformly stirred material at 25° C. for 6 hours under an inert gas, performing an in-situ terminal alkylation capping reaction, and obtaining a terminal alkoxy polysiloxane having a viscosity of 47700 mPa·s.

Comparative Example 2

A phenyl silicone resin and a preparation method thereof, comprising the following steps: dissolving hydroxyl-terminated methyltrifluoropropylsiloxane in toluene, then dripping it into a flask containing a mixed solution of dimethyldichlorosilane, toluene and diethylamine, stirring at 25°C for 1h under nitrogen protection, absorbing tail gas HC1 with a 1 mol/L sodium hydroxide aqueous solution after the reaction is completed to obtain a product, dripping all of the product into a mixed solution containing a phenyl silicone resin prepolymer and diethylamine, stirring at 10°C for 1h, filtering, then adding 100 parts of distilled water at 10°C, stirring for 30min, and drying to obtain the phenyl silicone resin.

The organosilicon resins obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were subjected to viscosity tests. The test method was in accordance with GB/T10247-2008. The test results are shown in Table 1 below.

Table 1 Comparison of viscosity, chlorine content and T _{d10% of} the silicone resins obtained in Examples 1 to 5 of the present invention and Comparative Examples 1 to 2

Resin viscosity (mPa·s) Chlorine content (wt%) _Td10％ (℃) 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 / /

It can be seen from the data in Table 1 that compared with Comparative Example 1 and Comparative Example 2, Comparative Example 1 is a terminal alkoxy-terminated polysiloxane synthesized by reacting hydroxyl polysiloxane with other siloxane monomers. Although there are hydroxyl and alkoxy reactive groups, the overall viscosity is relatively large, the fluidity is poor, and the reaction is relatively simple; Comparative Example 2 is a hydroxyl-terminated siloxane monomer that reacts with a chlorosilane monomer and water to release HCl, which is then mixed with a phenyl silicone resin prepolymer to obtain a high molecular weight, heat-resistant phenyl silicone resin (resistant to 300°C). Although the obtained phenyl silicone resin has excellent heat resistance, Si-Cl reacts violently with active hydrogen, and the prepared silicone resin contains almost no Cl, resulting in a reduction in its reactive groups. At the same time, the phenyl silicone resin has a high viscosity and is difficult to blend with other high-performance polymer materials. Only a small amount can be added thereto by physical blending, which greatly reduces its application scenarios.

The reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups obtained by the present invention has low viscosity and good heat resistance, and provides a basis for further adding other functional fillers; and the resin contains reactive groups hydroxyl and hydrocarbon chloride, and the hyperbranched silicone resin can be introduced into the resin through a chemical reaction by means of a nucleophilic substitution reaction to form a multiple cross-linked network, thereby improving the heat resistance, thermal stability, adhesion, flame retardancy and moisture resistance of the resin, and the content thereof can be flexibly adjusted within a large range, and is suitable for various different systems.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (10)

1. A method for preparing a reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbon groups, characterized in that a siloxane monomer containing chlorinated hydrocarbon groups and a siloxane monomer containing non-chlorinated hydrocarbon groups are used as raw materials, water is added for mixing and reaction, and then the siloxane monomer, water, a solvent and a catalyst are added for reaction to obtain a solution, and then a capping agent is added for end-capping, and the solution after the reaction is purified to obtain a reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbon groups. 2. The method for preparing a reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups according to claim 1, characterized in that the chlorinated hydrocarbon group-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 a reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbons 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, ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, and γ-glycidyloxypropyltrimethoxysilane. 4. The method for preparing a reactive heat-resistant chlorinated hydrocarbon-containing hyperbranched organosilicon resin according to claim 1, characterized in that the molar ratio of the chlorinated hydrocarbon-containing siloxane monomer to the non-chlorinated hydrocarbon-containing siloxane monomer is 0.01-0.99:0.99-0.01, and the molar ratio of the siloxane monomer to water is 1:0.5-3. 5. The method for preparing a reactive heat-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups according to claim 1, characterized in that the reaction temperature is 0 to 150°C and the reaction time is 1 to 36 hours. 6. The method for preparing a reactive heat-resistant chlorinated hydrocarbon-containing hyperbranched silicone 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 water, 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. 7. The method for preparing a reactive heat-resistant chlorinated hydrocarbon-containing hyperbranched silicone 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. 8. The method for preparing a reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbon groups according to any one of claims 1 to 7, characterized in that the steps are as follows: (1) mixing a siloxane monomer containing a chlorinated hydrocarbon group, a siloxane monomer containing a non-chlorinated hydrocarbon group and water, the reaction temperature being 0 to 150° C., the reaction time being 1 to 24 hours, the molar ratio of the siloxane monomer containing a chlorinated hydrocarbon group to the siloxane monomer containing a non-chlorinated hydrocarbon group being 0.01 to 0.99:0.99 to 0.01, and the molar ratio of the siloxane monomer to water being 1:0.5 to 3; (2) continuing to add siloxane monomers containing chlorinated hydrocarbon groups or siloxane monomers containing non-chlorinated hydrocarbon groups, water, solvents and catalysts; 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 the siloxane monomers, the reaction temperature is 0-150° C., the reaction time is 1-36 hours, and the molar ratio of siloxane monomers containing chlorinated hydrocarbon groups to siloxane monomers containing non-chlorinated hydrocarbon groups is 0.01-0.99:0.99-0.01; (3) adding a capping agent to the solution after condensation growth in step (2) to continue the reaction, wherein the molar ratio of the 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 after the reaction is completed, the solution is neutralized and filtered; (4) Purifying the solution after the reaction in step (3) to obtain a reactive temperature-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups. 9. A reactive heat-resistant hyperbranched organosilicon resin containing chlorinated hydrocarbon groups prepared by the method according to any one of claims 1 to 8. 10. Use of the reactive temperature-resistant hyperbranched silicone resin containing chlorinated hydrocarbon groups according to claim 9 in the preparation and modification of silicone polymers, special high molecular polymers and composite materials involved in the fields of aerospace, electronic packaging and transportation.