Hydrophilic hyperbranched organic silicon resin with side group containing phosphorus group and preparation method of hydrophilic hyperbranched organic silicon resin

Abstract

The invention discloses hydrophilic hyperbranched organic silicon resin with a side group containing a phosphorus group and a preparation method of the hydrophilic hyperbranched organic silicon resin, and belongs to the technical field of high polymer materials. The method comprises the following steps: synthesizing a phosphorus-containing silane coupling agent monomer from a phosphorus-containing compound monomer and an isocyanate-based silane coupling agent, and then carrying out hydrolytic condensation on the phosphorus-containing silane coupling agent monomer and the silane coupling agent monomer to prepare the hydrophilic hyperbranched organic silicon resin of which the side group contains the phosphorus group. The hyperbranched organic silicon resin prepared by the method is controllable in phosphorus content and active functional group content, is a low-viscosity transparent liquid material, is easy to process and use, and has excellent flame retardance and thermal stability; meanwhile, the preparation process is simple, reaction conditions are mild, and the flame retardant can be well dispersed in water, is environment-friendly and has an important application prospect in flame-retardant modification of water-based materials.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a hydrophilic hyperbranched silicone resin with a side phosphorus-containing group and a preparation method thereof. Background Art

[0002] At present, an effective way to improve the flame retardancy of materials is to add organic flame retardants, which can be divided into halogen flame retardants and non-halogen flame retardants. Halogen flame retardants are one of the largest organic flame retardants in the world. They are widely used due to their high flame retardant efficiency. However, their decomposition and combustion produce a large amount of smoke and toxic corrosive gases, which can easily cause "secondary disasters". Non-halogen flame retardants mainly include phosphorus flame retardants and silicon flame retardants. Phosphorus flame retardants have the advantages of low toxicity, high flame retardant efficiency, and green environmental protection. They quench free radicals in the gas phase and decompose to generate phosphoric acid, phosphate esters and other compounds to isolate oxygen, thereby achieving the effect of flame extinguishing. However, phosphorus flame retardants have poor thermal stability and are easy to decompose at high temperatures, which limits their further application. Silicon flame retardants have high thermal stability, but when used alone, the flame retardant effect is average, and they usually need to be used in conjunction with other types of flame retardants.

[0003] Hyperbranched silicone resin is a three-dimensional structure, a new type of polymer compound with Si-O-Si bonds as the main chain and organic groups connected to the side chains. Compared with traditional linear silicone resins, it has a higher degree of branching, so it has the advantages of low viscosity, high solubility, rich functional group structure and polymer cross-linking. Since the main chain of the hyperbranched silicone resin molecule contains a large number of Si-O-Si bonds and has a high bond energy, it has high thermal stability and good temperature resistance. In addition, it will produce a SiO2 protective layer to protect the material during the combustion and decomposition process. The organic functional groups of its side chains are optional, and the molecules are highly designable. Therefore, by designing the side chain organic groups into phosphorus-containing functional structures, hyperbranched silicone resins with phosphorus-containing side groups can be obtained, which can have both excellent thermal stability and excellent flame retardant properties.

[0004] Patent CN109912799A (publication date: 2019.06.21) discloses a phosphorus-containing silicone flame retardant prepared by using γ-aminopropyltriethoxysilane (KH-550), formaldehyde and phosphorous acid as raw materials, and simultaneously performing Mannich reaction and intermolecular cross-linking polymerization, which can play a good role in the synergistic flame retardancy of silicon and phosphorus, and is applied to PET materials to prepare PET flame-retardant composite materials, which can significantly improve the flame retardancy and smoke suppression performance of PET. Patent CN108997584A (publication date: 2018.12.14) discloses a phosphorus-nitrogen-containing silicone flame retardant obtained by reacting amino silicone oil and chlorophosphate compounds. The synthesized flame retardant has good thermal stability, is non-toxic, can improve the processability of plastics, and has little effect on the mechanical properties of the substrate. Patent CN109734914A (publication date: 2019.05.10) discloses a phosphorus-modified silicone resin of the corresponding structure obtained by hydrolyzing and polymerizing phosphate or phosphite with silane containing different numbers of alkoxy groups under heating and acid catalyst. Patent CN116444571A (publication date: 2023.07.18) discloses a phosphorus-nitrogen-containing silicone flame retardant synthesized from p-hydroxybenzaldehyde, hexachlorocyclotriphosphazene and KH550 as raw materials, which improves the stability, flame retardant properties and polymer compatibility of the flame retardant through multi-element synergy.

[0005] At present, the silicon-phosphorus synergistic flame retardancy reported in related articles and patents is mostly linear structure or small molecule structure. Materials with this structure have certain defects in thermal stability and water resistance. There are few related studies on hydrophilic hyperbranched silicone resins containing phosphorus in the side groups. In addition, people are paying more and more attention to green environmental protection, so water-based materials are becoming more and more important, but there are currently no patent reports on hydrophilic phosphorus-containing hyperbranched silicone resins. Hyperbranched silicone can be designed with richer functional groups due to its unique structure. When introducing phosphorus-containing groups, some reactive functional groups can also be introduced, providing a higher crosslinking density when modifying the flame retardant properties of the material to improve the mechanical and flame retardant properties of the material. In addition, hyperbranched silicone contains a large number of Si-O-Si bonds, has high thermodynamic stability, and can form a protective layer to protect the material during the combustion process. Therefore, it is of great significance to design a hydrophilic phosphorus-containing hyperbranched silicone resin. Summary of the invention

[0006] The technical problem solved by the present invention is to provide a preparation method of a hydrophilic hyperbranched silicone resin having a side group containing phosphorus groups; another technical problem to be solved by the present invention is to provide a hydrophilic hyperbranched silicone resin having a side group containing phosphorus groups.

[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0008] A method for preparing a hydrophilic hyperbranched silicone resin having a side phosphorus-containing group, the specific steps are as follows:

[0009] 1) adding a phosphorus-containing monohydric alcohol or polyhydric alcohol monomer A and an isocyanate silane coupling agent monomer B into a reactor, wherein the molar ratio of monomer A to monomer B is 1:1 to 3:1, adding a catalyst for reaction, the reaction temperature is 30 to 150° C., and the reaction time is 1 to 24 hours to obtain compound 1;

[0010] 2) adding silane coupling agent monomer C and water to the system for hydrolysis reaction, the reaction temperature of the hydrolysis is 20-100° C., the reaction time is 1-24 hours, the molar ratio of compound 1 to monomer C is 0.01-0.99:0.99-0.01, and the molar ratio of silane coupling agent to water is 1:0.5-3;

[0011] 3) After hydrolysis, a catalyst and a solvent are added to carry out condensation reaction growth, the reaction temperature is 20 to 150° C., and the reaction time is 1 to 36 hours;

[0012] 4) after the reaction is completed, performing a reduced pressure distillation purification treatment to obtain a hydrophilic hyperbranched silicone resin having a side phosphorus-containing group;

[0013] The reaction formula is as follows:

[0014]

[0015] Wherein, R1 is -CH2PO(OCH2CH3)2, -CH2CH2PO(OCH3)2, -CH2PO(CH2OH)2, One of -CH2CH2N(CH2CH2OH)CH2PO(OCH2CH3)2, -CH2NHCOCH2CH2PO(OCH3)2;

[0016] R2 is one of -CH2 and -CH2CH3;

[0017] R is selected from -CH3, -CH2CH3, -CH2CH2CH2CH2NH2, -CH=CH2

[0018] Among them, R at different positions are the same or different;

[0019] R' is -CH2CH2CH2NHCOOCH2PO(CH2OH)2, -CH2CH2CH2NHCOOCH2CH2PO(OCH3)2, -CH2CH2CH2NHCOOCH2PO(OCH2CH3)2, -CH2CH2CH2NHCOOCH2CH2N(CH2CH2OH)CH2PO(OCH2CH3)2 ,-CH2CH2CH2NHCOOCH2NHCOCH2CH2PO(OCH3)2, One of them.

[0020] In the step 1), the monomer A is selected from one or more of diethyl hydroxymethyl phosphate, dimethyl hydroxyethyl phosphate, trishydroxymethyl phosphine oxide, pentaerythritol phosphate, diethyl N,N-bis(2-hydroxyethyl)aminomethylenephosphonate, and dimethyl [3-[(hydroxymethyl)amino]-3-carbonylpropyl]-phosphonate.

[0021] In the step 1), monomer B is selected from one or more of 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane;

[0022] The catalyst in step 1) is selected from one or more of dibutyltin dilaurate, stannous octoate, cobalt octoate, lead octoate, iron octoate, zinc naphthenate, and tetrabutyl titanate.

[0023] In the step 2), the silane coupling agent monomer C is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, benzylaminomethyltriethoxysilane and benzylaminomethyltrimethoxysilane.

[0024] The water in step 2) is one or more of distilled water, deionized water and purified water.

[0025] In step 3), the solvent is selected from one or more of tetrahydrofuran, acetone, dichloromethane, ethyl acetate, toluene, ethanol, N-methylpyrrolidone, and N,N-dimethylformamide.

[0026] In step 3), the catalyst is selected from one or more of phosphoric acid, hydrochloric acid, benzenesulfonic acid, sodium hydroxide, triethylamine, ammonia water, and tetramethylammonium hydroxide.

[0027] The method prepares a hydrophilic hyperbranched organic silicon resin having a side group containing phosphorus groups.

[0028] The hydrophilic hyperbranched silicone resin containing phosphorus groups on the side groups is used in the preparation of flame retardant materials.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] (1) The hydrophilic hyperbranched silicone with phosphorus-containing side groups prepared by the present invention has a highly cross-linked structure with Si-O-Si bonds as the main chain, and has high thermal stability. During the combustion process, a SiO2 protective layer can be generated to protect the internal materials. In addition, due to its unique three-dimensional multi-branched structure, it can ensure its high cross-linking while exhibiting the characteristics of low viscosity and high solubility. It has good compatibility when modifying materials such as polyurethane and epoxy resin, and can improve their mechanical properties and thermal stability.

[0031] (2) The present invention synthesizes a hydrophilic hyperbranched silicone resin having a phosphorus-containing side group by a hydrolysis condensation method. Therefore, the organic functional groups of the hyperbranched side chains can be designed during the synthesis process. The organic functional groups can be chemically inert alkyl, phenyl and other groups, or can be designed to contain active functional groups such as amino groups, or other functional groups. The designability is strong, and the molecular structure can be easily designed and regulated.

[0032] (3) The hyperbranched silicone resin synthesized by the present invention contains a large amount of phosphorus and silicon elements, can well achieve the synergistic flame retardant effect of silicon and phosphorus, has good hydrophilicity, has a good dispersion effect in water, has important application prospects in the flame retardant modification of water-based materials, and can be used to prepare flame retardant materials; and the synthesis conditions are mild, no toxic and hazardous products are produced, the preparation method is simple, and can be scaled up for production. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The actual pictures of the hydrophilic hyperbranched silicone resins with phosphorus-containing side groups prepared in Examples 1 to 7;

[0034] Figure 2 A hydrophilic hyperbranched silicone resin having a phosphorus-containing side group prepared in Example 1 and a physical picture of the resin dispersed in water;

[0035] Figure 3 This is a dynamic light scattering test particle size distribution diagram of the hydrophilic hyperbranched silicone resin with phosphorus-containing side groups prepared in Example 1 dispersed in water;

[0036] Figure 4 Thermogravimetric curve of the hydrophilic hyperbranched silicone resin containing phosphorus groups on the side groups prepared in Example 1;

[0037] Figure 5 This is the full XPS spectrum of the hydrophilic hyperbranched silicone resin with phosphorus-containing side groups prepared in Example 1;

[0038] Figure 6The actual pictures are of unmodified polyurethane and the hydrophilic hyperbranched organosilicon-modified polyurethane emulsion with phosphorus-containing side groups prepared in Example 1;

[0039] Figure 7 The actual pictures are of unmodified polyurethane and the hydrophilic hyperbranched organosilicon-modified polyurethane cured film with phosphorus-containing side groups prepared in Example 1;

[0040] Figure 8 This is the combustion test diagram of unmodified waterborne polyurethane;

[0041] Fig. 9 This is a combustion test diagram of the hydrophilic hyperbranched silicone resin modified waterborne polyurethane with phosphorus-containing side groups prepared in Example 1. DETAILED DESCRIPTION

[0042] The present invention is further illustrated below in conjunction with specific examples. The examples are implemented based on the technical solutions of the present invention. It should be understood that these examples are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0043] Example 1

[0044] A method for preparing a hydrophilic hyperbranched silicone resin containing a phosphorus group on the side group:

[0045] (1) 16.8 g of diethyl hydroxymethyl phosphate and 24.7 g of isocyanate triethoxysilane were added to a reactor, and 0.15 g of dibutyltin dilaurate was added and reacted at 80° C. for 4 h;

[0046] (2) adding 11.8 g of γ-glycidyloxypropyltrimethoxysilane, 8.6 g of methyltrimethoxysilane and 4.7 g of distilled water to the system for hydrolysis reaction at room temperature for 4 h;

[0047] (3) Then, 50 mL of N-methylpyrrolidone and 1.5 mL of 0.1 mol / L NaOH solution were added to the system and reacted at 150 °C for 1 h;

[0048] (4) After the reaction is completed, the solvent and small molecules are removed by vacuum distillation to obtain a phosphorus-containing hyperbranched silicone resin, which is recorded as resin 1.

[0049] Example 2

[0050] A method for preparing a hydrophilic hyperbranched silicone resin containing a phosphorus group on the side group:

[0051] (1) 45.6 g of pentaerythritol phosphate and 24.7 g of isocyanate triethoxysilane were added to a reactor, and 0.1 g of tetrabutyl titanate was added and reacted at 150° C. for 1 h;

[0052] (2) adding 18.9 g of benzylaminomethyl triethoxysilane, 6 g of ethyl trimethoxysilane and 3.8 g of deionized water to the system and performing a hydrolysis reaction at 70° C. for 24 h;

[0053] (3) Then, 50 mL of dichloromethane and 1.05 g of triethylamine were added to the system and reacted at 120 °C for 36 h;

[0054] (4) After the reaction is completed, the solvent and small molecules are removed by vacuum distillation to obtain a phosphorus-containing hyperbranched organosilicon resin, which is recorded as resin 2.

[0055] Example 3

[0056] A method for preparing a hydrophilic hyperbranched silicone resin containing a phosphorus group on the side group:

[0057] (1) 14 g of trimethylolphosphine oxide and 49.4 g of isocyanate triethoxysilane were added to a reaction vessel, and 0.2 g of stannous octoate was added and reacted at 100° C. for 8 h;

[0058] (2) adding 24 g of phenyltriethoxysilane, 9.4 g of methyltriethoxysilane and 10.8 g of purified water to the system and performing a hydrolysis reaction at 60° C. for 10 h;

[0059] (3) Then, 50 mL of tetrahydrofuran and 0.825 mL of HCl were added to the system and reacted at 90 °C for 12 h;

[0060] (4) After the reaction is completed, the solvent and small molecules are removed by vacuum distillation to obtain a phosphorus-containing hyperbranched organosilicon resin, which is recorded as resin 3.

[0061] Example 4

[0062] A method for preparing a hydrophilic hyperbranched silicone resin containing a phosphorus group on the side group:

[0063] (1) 25.5 g of diethyl N,N-bis(2-hydroxyethyl)aminomethylenephosphonate and 37.1 g of isocyanatetriethoxysilane were added to a reactor, and 0.1 g of lead octoate was added and reacted at 120° C. for 12 h;

[0064] (2) adding 13.5 g of aminopropyltriethoxysilane, 8.2 g of ethyltriethoxysilane, 12.3 g of phenyltrimethoxysilane and 9.0 g of deionized water to the system and performing a hydrolysis reaction at 50° C. for 12 h;

[0065] (3) Then, 50 mL of toluene and 1.2 g of tetramethylammonium hydroxide were added to the system and reacted at 100 °C for 12 h;

[0066] (4) After the reaction is completed, the solvent and small molecules are removed by vacuum distillation to obtain a phosphorus-containing hyperbranched organosilicon resin, which is recorded as resin 4.

[0067] Example 5

[0068] A method for preparing a hydrophilic hyperbranched silicone resin having a side phosphorus group:

[0069] (1) 21.1 g of dimethyl [3-[(hydroxymethyl)amino]-3-carbonylpropyl]-phosphonate and 20.5 g of isocyanate trimethoxysilane were added to a reactor, and 0.15 g of zinc cyclohexaneate was added and reacted at 60° C. for 24 h;

[0070] (2) adding 6.8 g of ethyltrimethoxysilane, 8.6 g of γ-glycidyloxypropyltriethoxysilane and 5.4 g of purified water to the system for hydrolysis reaction at room temperature for 4 h;

[0071] (3) Then, 50 mL of acetone and 1.2 g of ammonia water were added to the system and reacted at 130 °C for 6 h;

[0072] (4) After the reaction is completed, the solvent and small molecules are removed by vacuum distillation to obtain a phosphorus-containing hyperbranched organosilicon resin, which is recorded as resin 5.

[0073] Example 6

[0074] A method for preparing a hydrophilic hyperbranched silicone resin having a side phosphorus group:

[0075] (1) 15.4 g of dimethyl hydroxyethylphosphonate and 20.5 g of isocyanate trimethoxysilane were added to a reaction vessel, and 0.15 g of cobalt octoate was added to react at room temperature for 6 h;

[0076] (2) adding 17.8 g of methyltriethoxysilane, 12.8 g of aminopropyltrimethoxysilane and 5.4 g of distilled water to the system for hydrolysis reaction at room temperature for 2 h;

[0077] (3) Then, 50 mL of ethanol and 1.2 g of phosphoric acid were added to the system and reacted at 90 °C for 12 h;

[0078] (4) After the reaction is completed, the solvent and small molecules are removed by vacuum distillation to obtain a phosphorus-containing hyperbranched organosilicon resin, which is referred to as resin 6.

[0079] Example 7

[0080] A method for preparing a hydrophilic hyperbranched silicone resin having a side phosphorus group:

[0081] (1) 16.8 g of diethyl hydroxymethyl phosphate and 24.7 g of isocyanate triethoxysilane were added to a reactor, and 0.1 g of iron octanoate was added and reacted at 100° C. for 24 h;

[0082] (2) adding 14.8 g of vinyl trimethoxysilane, 12 g of benzyl aminomethyl triethoxysilane and 3.6 g of pure water to the system and performing a hydrolysis reaction at 60° C. for 2 h;

[0083] (3) Then, 50 mL of N,N-dimethylformamide and 1.5 g of benzenesulfonic acid were added to the system and reacted at 100 °C for 12 h;

[0084] (4) After the reaction is completed, the solvent and small molecules are removed by vacuum distillation to obtain a phosphorus-containing hyperbranched organosilicon resin, which is recorded as resin 7.

[0085] Table 1

[0086] Resin viscosity (mPa·s) Phosphorus content (wt%) Example 1 287 6.62 Example 2 298 2.73 Example 3 328 3.33 Example 4 265 3.53 Example 5 343 6.21 Example 6 319 6.67 Example 7 173 5.45

[0087] Table 1 shows the viscosity and phosphorus content of the hydrophilic hyperbranched silicone resin with phosphorus-containing side groups. It can be seen that the hyperbranched resin has a low viscosity and good modification processing conditions. In addition, the phosphorus content is controllable and can be changed by molecular structure design.

[0088] Figure 1 It can be seen from the actual pictures that transparent hydrophilic hyperbranched silicone resins containing phosphorus in the side groups can be synthesized from Examples 1-9.

[0089] Figure 2 (Left) is a physical picture of the phosphorus-containing hyperbranched organosilicon prepared in Example 1. Figure 2 (Right picture) is a physical picture of the phosphorus-containing hyperbranched organosilicon prepared in Example 1 dispersed in water. It can be seen that the prepared phosphorus-containing hyperbranched organosilicon has good dispersibility in water.

[0090] Figure 3 It can be seen that the particle size distribution of the phosphorus-containing hyperbranched organosilicon prepared in Example 1 dispersed in water has an average particle size of about 25 nm, indicating that the phosphorus-containing hyperbranched organosilicon can form an emulsion in water.

[0091] Figure 4 It can be seen that the initial thermal decomposition temperature of the phosphorus-containing hyperbranched organosilicon prepared in Example 1 under N2 atmosphere is about 265°C, and the residual weight at 1000°C is 45%, which has good thermal stability.

[0092] Figure 5 It can be proved that the phosphorus-containing hyperbranched organosilicon prepared in Example 1 contains C, O, P, and Si elements, wherein the P element accounts for about 6%.

[0093] Figure 6(Left picture) is a physical picture of unmodified polyurethane emulsion. Figure 6 (Right picture) is a physical picture of the phosphorus-containing hyperbranched silicone-modified polyurethane emulsion prepared in Example 1. It can be seen that the modified polyurethane emulsion appears slightly blue, indicating that the emulsion has better dispersibility.

[0094] Figure 7 (Left picture) is a physical picture of the unmodified polyurethane curing. Figure 7 (Right picture) is a physical picture of the cured phosphorus-containing hyperbranched silicone-modified polyurethane prepared in Example 1. It can be seen that both have good optical transmittance, indicating that the prepared phosphorus-containing hyperbranched silicone and polyurethane have good compatibility.

[0095] Figure 8 This is a schematic diagram of the ignition of unmodified polyurethane. It can be seen that the unmodified polyurethane will continue to burn and there will be a lot of debris.

[0096] Fig. 9 This is a schematic diagram of the ignition of the phosphorus-containing hyperbranched silicone-modified polyurethane prepared in Example 1. It can be seen that the light is on and then quickly extinguished within 3 seconds, showing good flame retardancy, indicating that the prepared phosphorus-containing hyperbranched silicone has a significant improvement in the flame retardancy of waterborne polyurethane.

[0097] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A hydrophilic hyperbranched silicone resin containing phosphorus groups on the side groups and a preparation method thereof, characterized in that: The specific steps are as follows: 1) adding a phosphorus-containing monohydric alcohol or polyhydric alcohol monomer A and an isocyanate silane coupling agent monomer B into a reactor, wherein the molar ratio of monomer A to monomer B is 1:1 to 3:1, adding a catalyst for reaction, the reaction temperature is 30 to 150° C., and the reaction time is 1 to 24 hours to obtain compound 1; 2) adding silane coupling agent monomer C and water to the system for hydrolysis reaction, the reaction temperature of the hydrolysis is 20-100° C., the reaction time is 1-24 hours, the molar ratio of compound 1 to monomer C is 0.01-0.99:0.99:0.01, and the molar ratio of silane coupling agent to water is 1:0.5-3; 3) After hydrolysis, a catalyst and a solvent are added to carry out condensation reaction growth, the reaction temperature is 20 to 150° C., and the reaction time is 1 to 36 hours; 4) after the reaction is completed, performing a reduced pressure distillation purification treatment to obtain a hydrophilic hyperbranched silicone resin having a side phosphorus-containing group; The reaction formula is as follows: Wherein, R1 is -CH2PO(OCH2CH3)2, -CH2CH2PO(OCH3)2, -CH2PO(CH2OH)2, One of -CH2CH2N(CH2CH2OH)CH2PO(OCH2CH3)2, -CH2NHCOCH2CH2PO(OCH3)2; R2 is one of -CH2 and -CH2CH3; R is selected from -CH3, -CH2CH3, -CH2CH2CH2CH2NH2, -CH=CH2, Among them, R at different positions are the same or different; R' is -CH2CH2CH2NHCOOCH2PO(CH2OH)2, -CH2CH2CH2NHCOOCH2CH2PO(OCH3)2, -CH2CH2CH2NHCOOCH2PO(OCH2CH 3)2, -CH2CH2CH2NHCOOCH2CH2N(CH2CH2OH)CH2PO(OCH2CH3)2, -CH2CH2CH2NHCOOCH2NHCOCH2CH2PO(OCH3)2, One of them.

2. The method for preparing a hydrophilic hyperbranched silicone resin having a side phosphorus-containing group according to claim 1, characterized in that: In the step 1), the monomer A is selected from one or more of diethyl hydroxymethyl phosphate, dimethyl hydroxyethyl phosphate, trishydroxymethyl phosphine oxide, pentaerythritol phosphate, diethyl N,N-bis(2-hydroxyethyl)aminomethylenephosphonate, and dimethyl [3-[(hydroxymethyl)amino]-3-carbonylpropyl]-phosphonate.

3. The method for preparing a hydrophilic hyperbranched silicone resin having a side phosphorus-containing group according to claim 1, characterized in that: In the step 1), the monomer B is selected from one or more of 3-isocyanatepropyltriethoxysilane and 3-isocyanatepropyltrimethoxysilane.

4. The method for preparing a hydrophilic hyperbranched silicone resin having a side phosphorus-containing group according to claim 1, characterized in that: In the step 1), the catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, cobalt octoate, lead octoate, iron octoate, zinc naphthenate, and tetrabutyl titanate.

5. The method for preparing a hydrophilic hyperbranched silicone resin having a side phosphorus-containing group according to claim 1, characterized in that: In the step 2), the silane coupling agent monomer C is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, benzylaminomethyltriethoxysilane and benzylaminomethyltrimethoxysilane.

6. The method for preparing a hydrophilic hyperbranched silicone resin having a side phosphorus-containing group according to claim 1, characterized in that: The water in step 2) is one or more of distilled water, deionized water and purified water.

7. The method for preparing a hydrophilic hyperbranched silicone resin having a side phosphorus-containing group according to claim 1, characterized in that: In step 3), the solvent is selected from one or more of tetrahydrofuran, acetone, dichloromethane, ethyl acetate, toluene, ethanol, N-methylpyrrolidone, and N,N-dimethylformamide.

8. The method for preparing a hydrophilic hyperbranched silicone resin having a side phosphorus-containing group according to claim 1, characterized in that: In step 3), the catalyst is selected from one or more of phosphoric acid, hydrochloric acid, benzenesulfonic acid, sodium hydroxide, triethylamine, ammonia water, and tetramethylammonium hydroxide.

9. A hydrophilic hyperbranched silicone resin having a phosphorus-containing side group prepared according to the method of any one of claims 1 to 8.

10. Use of the hydrophilic hyperbranched silicone resin having phosphorus-containing side groups according to claim 9 in the preparation of flame retardant materials.

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