A hydrophilic hyperbranched silicone resin having a pendant phosphorus group and a method for preparing the same

Abstract

The application discloses a hydrophilic hyperbranched organosilicon resin with a side group containing a phosphorus group and a preparation method thereof, and belongs to the technical field of high polymer materials. The method is to synthesize a silane coupling agent monomer containing phosphorus by coupling a phosphorus compound monomer and an isocyanate silane coupling agent, and then to hydrolyze and condense the silane coupling agent monomer containing phosphorus to obtain the hydrophilic hyperbranched organosilicon resin with the side group containing the phosphorus group. The hyperbranched organosilicon resin prepared by the method is a low-viscosity transparent liquid material, and has controllable phosphorus content and active functional group content, is easy to process and use, has excellent flame retardance and thermal stability, and has important application prospects in the flame-retardant modification of water-based materials.

Description

Technical Field

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

[0002] Currently, an effective way to improve the flame retardancy of materials is to add organic flame retardants, which can be divided into halogen-based and non-halogen-based flame retardants. Halogen-based flame retardants are among the world's most produced organic flame retardants and are widely used due to their high flame retardant efficiency. However, their decomposition and combustion produce large amounts of smoke and toxic and corrosive gases, which can easily cause "secondary disasters." Non-halogen-based flame retardants mainly include phosphorus-based flame retardants and silicon-based flame retardants. Phosphorus-based flame retardants offer the advantages of low toxicity, high flame retardant efficiency, and environmental friendliness. They achieve flame extinguishing effects by quenching free radicals in the gas phase and decomposing to generate compounds such as phosphoric acid and phosphate esters, which isolate oxygen. However, the poor thermal stability of phosphorus-based flame retardants and their susceptibility to high-temperature decomposition limit their further application. Silicon-based flame retardants have high thermal stability, but their flame retardant effect is limited when used alone, and they are usually used in combination with other types of flame retardants.

[0003] Hyperbranched silicone resins are a new class of polymers with a three-dimensional structure, characterized by Si-O-Si bonds as the backbone and organic groups attached to the side chains. Compared to traditional linear silicone resins, they have a higher degree of branching, resulting in low viscosity, high solubility, a rich functional group structure, and high molecular weight crosslinking. Because hyperbranched silicone resins contain a large number of Si-O-Si bonds in their main chain, their high bond energy provides them with high thermal stability and excellent temperature resistance. During combustion and decomposition, they produce a protective SiO2 layer to protect the material. The organic functional groups in their side chains are optional, making the molecules highly designable. Therefore, designing the side chain organic groups to contain phosphorus-containing functional structures can produce hyperbranched silicone resins with phosphorus-containing side groups, which combine excellent thermal stability with outstanding flame retardancy.

[0004] A phosphorus-containing organosilicon flame retardant was prepared by simultaneously performing Mannich reaction and intermolecular crosslinking polymerization using gamma-aminopropyl triethoxysilane (KH-550), formaldehyde and phosphorous acid as raw materials, which can well play the synergistic flame-retardant effect of silicon and phosphorus, and can be applied to PET material to prepare a PET flame-retardant composite, which can significantly improve the flame-retardant performance and smoke suppression performance of PET. In patent CN108997584A (publication date: 2018.12.14), an organosilicon flame retardant containing phosphorus and nitrogen is obtained by reacting amino silicone oil and chlorophosphonate compounds, which has good thermal stability, is non-toxic, can improve plastic processability, and has little effect on the mechanical properties of the substrate. In patent CN109734914A (publication date: 2019.05.10), a phosphorus-modified organosilicon resin with the corresponding structure is obtained by hydrolytic polymerization of phosphate or phosphite ester and silane containing different number of alkoxy groups under the action of heating and acid catalyst. In patent CN116444571A (publication date: 2023.07.18), a phosphorus and nitrogen-containing organosilicon flame retardant is synthesized using p-hydroxybenzaldehyde, hexachlorocyclotriphosphazene and KH550 as raw materials, which improves the stability, flame-retardant performance and compatibility of high molecular weight of the flame retardant through multi-element synergistic effect.

[0005] Most of the current related articles and patents report on silicon-phosphorus synergistic flame retardants, which are mostly linear structures or small molecule structures. Such structures have certain defects in terms of thermal stability and water resistance. There is little research on hydrophilic hyperbranched organosilicon resins with side groups containing phosphorus. Moreover, people are increasingly emphasizing green and environmental protection, so water-based materials are becoming increasingly important. However, there is no patent report on hydrophilic phosphorus-containing hyperbranched organosilicon resins. Hyperbranched organosilicon can be designed with more functional groups due to its unique structure, and can introduce reactive functional groups while introducing phosphorus-containing groups, which can provide higher crosslinking density when modifying the flame-retardant performance of materials, thereby improving the mechanical properties and flame-retardant properties of the materials. In addition, hyperbranched organosilicon contains a large number of Si-O-Si bonds, which have high thermodynamic stability and can form a protective layer to protect the material during combustion. Therefore, it is of great significance to design a hydrophilic phosphorus-containing hyperbranched organosilicon resin. SUMMARY

[0006] The technical problem solved by the present application is to provide a preparation method of a hydrophilic hyperbranched organosilicon resin with side groups containing phosphorus groups. Another technical problem to be solved by the present application is to provide a hydrophilic hyperbranched organosilicon resin with side groups containing phosphorus groups.

[0007] To solve the above technical problems, the technical solutions adopted by the present application are as follows:

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

[0009] 1) The phosphorus-containing monoalcohol or polyalcohol monomer A and the isocyanate silane coupling agent monomer B are added to the reactor, the molar ratio of monomer A to monomer B is 1:1-3:1, a catalyst is added for reaction, the reaction temperature is 30-150℃, the reaction time is 1-24h, and compound 1 is obtained;

[0010] 2) The silane coupling agent monomer C and water are added to the system for hydrolysis reaction, the hydrolysis reaction temperature is 20-100℃, the reaction time is 1-24h, 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 for condensation reaction growth, the reaction temperature is 20-150℃, and the reaction time is 1-36h;

[0012] 4) After the reaction is completed, a vacuum distillation purification treatment is performed to obtain a hydrophilic hyperbranched silicone resin with a side group containing a phosphorus group;

[0013] The reaction formula is as follows:

[0014]

[0015] In the formula, R1 is one of -CH2PO(OCH2CH3)2, -CH2CH2PO(OCH3)2, -CH2PO(CH2OH)2, -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] Wherein, R at different positions is the same or different;

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

[0020] The monomer A in the step 1) is selected from one or more of hydroxymethyl phosphonic diethyl ester, hydroxyethyl phosphonic dimethyl ester, trimethylol phosphine oxide, pentaerythritol phosphonate, N,N-bis(2-hydroxyethyl)aminomethylene phosphonic diethyl ester, [3-[(hydroxymethyl)amino]-3-carbonylpropyl]-phosphonic dimethyl ester.

[0021] The monomer B in the step 1) is selected from one or more of 3-isocyanate propyl triethoxysilane, 3-isocyanate propyl trimethoxysilane;

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

[0023] The silane coupling agent monomer C in the step 2) is selected from one or more of methyl trimethoxysilane, methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, vinyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, aminopropyl trimethoxysilane, aminopropyl triethoxysilane, phenylaminomethyl triethoxysilane, phenylaminomethyl trimethoxysilane.

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

[0025] The solvent in the step 3) is selected from one or more of tetrahydrofuran, acetone, dichloromethane, ethyl acetate, toluene, ethanol, N-methyl pyrrolidone, N,N-dimethyl formamide.

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

[0027] The hydrophilic hyperbranched silicone resin with side groups containing phosphorus groups prepared by the method.

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

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

[0030] (1) The hydrophilic hyperbranched organosilicon prepared by the present application has a high crosslinking structure with Si-O-Si bond as the main chain, and has high thermal stability. In the combustion process, the SiO2 protective layer can be generated to protect the internal material. Due to the unique three-dimensional multi-branch structure, the high crosslinking structure can ensure low viscosity and high solubility, and has good compatibility when modifying polyurethane, epoxy resin and other materials, and can improve the mechanical properties and thermal stability.

[0031] (2) The hydrophilic hyperbranched organosilicon resin containing phosphorus group prepared by the present application is synthesized by hydrolysis and condensation method, so that the organic functional groups of the hyperbranched side chain can be designed in the synthesis process. It can be alkyl, phenyl and other groups with chemical inertness, or amino groups with active functional groups, or other functional groups. The designability is strong, and the molecular structure can be simply designed and controlled.

[0032] (3) The hyperbranched organosilicon resin synthesized by the present application contains a large amount of phosphorus and silicon elements, which can well realize the synergistic flame-retardant effect of silicon and phosphorus, has good hydrophilicity, has good dispersion effect in water, and has important application prospect in water-based material flame-retardant modification. It can be used for preparing flame-retardant materials; and the synthesis condition is mild, no toxic and harmful hazardous products are produced, the preparation method is simple, and the production can be scaled up. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 The actual picture of the hydrophilic hyperbranched organosilicon resin containing phosphorus group prepared for Examples 1-7 is shown in the figure;

[0034] Figure 2 The actual picture of the hydrophilic hyperbranched organosilicon resin containing phosphorus group prepared for Example 1 and dispersed in water is shown in the figure;

[0035] Figure 3 The dynamic light scattering test particle size distribution graph of the hydrophilic hyperbranched organosilicon resin containing phosphorus group prepared for Example 1 dispersed in water is shown in the figure;

[0036] Figure 4 The thermogravimetric curve graph of the hydrophilic hyperbranched organosilicon resin containing phosphorus group prepared for Example 1 is shown in the figure;

[0037] Figure 5 The XPS full spectrum graph of the hydrophilic hyperbranched organosilicon resin containing phosphorus group prepared for Example 1 is shown in the figure;

[0038] Figure 6A photograph of a cured film of an unmodified polyurethane and a hydrophilic hyperbranched organosilicon modified polyurethane emulsion prepared in Example 1 having a side group containing a phosphorus group;

[0039] Figure 7 A photograph of a cured film of an unmodified polyurethane and a hydrophilic hyperbranched organosilicon modified polyurethane emulsion prepared in Example 1 having a side group containing a phosphorus group;

[0040] Figure 8 A photograph of a combustion test of an unmodified waterborne polyurethane;

[0041] Figure 9 A photograph of a combustion test of a hydrophilic hyperbranched organosilicon resin modified waterborne polyurethane prepared in Example 1 having a side group containing a phosphorus group. DETAILED DESCRIPTION

[0042] The application is further illustrated below in conjunction with specific examples, which are implemented on the premise of the technical solutions of the application and are understood to be used for illustrating the application rather than limiting the scope of the application.

[0043] Example 1

[0044] A method for preparing a hydrophilic hyperbranched organosilicon resin having a side group containing a phosphorus group:

[0045] (1) 16.8 g of hydroxymethyl phosphonic acid diethyl ester and 24.7 g of isocyanate triethoxysilane were added to a reactor, 0.15 g of dibutyltin dilaurate was added, and the reaction was carried out at 80°C for 4 h;

[0046] (2) 11.8 g of γ-glycidoxypropyltrimethoxysilane, 8.6 g of methyltrimethoxysilane, and 4.7 g of distilled water were added to the system, and the hydrolysis reaction was carried out 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 the reaction was carried out at 150°C for 1 h;

[0048] (4) After the reaction was completed, the solvent and small molecules were removed by vacuum distillation purification treatment, and a phosphorus-containing hyperbranched organosilicon resin was obtained, which was recorded as Resin 1.

[0049] Example 2

[0050] A method for preparing a hydrophilic hyperbranched organosilicon resin having a side group containing a phosphorus group:

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

[0052] (2) To the system, 18.9 g of phenylaminomethyl triethoxysilane, 6 g of ethyl trimethoxysilane and 3.8 g of deionized water were added, and hydrolysis reaction was carried out at 70°C for 24 h;

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

[0054] (4) After the reaction was completed, purification treatment by reduced pressure distillation was carried out to remove the solvent and small molecules, and a phosphorus-containing hyperbranched silicone resin was obtained, which was denoted as Resin 2.

[0055] Example 3

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

[0057] (1) 14 g of trimethylol phosphate and 49.4 g of isocyanate group triethoxysilane were added to a reaction vessel, and 0.2 g of stannous octoate was added, and reaction was carried out at 100°C for 8 h;

[0058] (2) To the system, 24 g of phenyl triethoxysilane, 9.4 g of methyl triethoxysilane and 10.8 g of pure water were added, and hydrolysis reaction was carried out at 60°C for 10 h;

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

[0060] (4) After the reaction was completed, purification treatment by reduced pressure distillation was carried out to remove the solvent and small molecules, and a phosphorus-containing hyperbranched silicone resin was obtained, which was denoted as Resin 3.

[0061] Example 4

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

[0063] (1) 25.5 g of N,N-bis(2-hydroxyethyl) aminomethylene phosphonic acid diethyl ester and 37.1 g of isocyanate group triethoxysilane were added to a reactor, and 0.1 g of lead octoate was added, and reaction was carried out at 120°C for 12 h;

[0064] (2) To the system, 13.5 g of aminopropyl triethoxysilane, 8.2 g of ethyl triethoxysilane, 12.3 g of phenyl trimethoxysilane and 9.0 g of deionized water were added, and hydrolysis reaction was carried out at 50°C for 12 h;

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

[0066] (4) After the reaction is completed, the solvent and small molecules are removed by purification treatment of reduced pressure distillation to obtain a phosphorus-containing hyperbranched silicone resin, which is denoted as Resin 4.

[0067] Example 5

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

[0069] (1) 21.1 g of [3-[(hydroxymethyl)amino]-3-carbonylpropyl] dimethyl phosphonate and 20.5 g of isocyanate trimethoxysilane are added to a reactor, 0.15 g of zinc naphthenate is added, and reaction is performed at 60°C for 24 h;

[0070] (2) 6.8 g of ethyl trimethoxysilane, 8.6 g of γ-glycidoxypropyl triethoxysilane, and 5.4 g of distilled water are added to the system, and hydrolysis reaction is performed at room temperature for 4 h;

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

[0072] (4) After the reaction is completed, the solvent and small molecules are removed by purification treatment of reduced pressure distillation to obtain a phosphorus-containing hyperbranched silicone resin, which is denoted as Resin 5.

[0073] Example 6

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

[0075] (1) 15.4 g of hydroxyethyl dimethyl phosphonate and 20.5 g of isocyanate trimethoxysilane are added to a reaction container, 0.15 g of cobalt octoate is added, and reaction is performed at room temperature for 6 h;

[0076] (2) 17.8 g of methyl triethoxysilane, 12.8 g of aminopropyl trimethoxysilane, and 5.4 g of distilled water are added to the system, and hydrolysis reaction is performed at room temperature for 2 h;

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

[0078] (4) After the reaction is completed, the solvent and small molecules are removed by purification treatment of reduced pressure distillation to obtain a phosphorus-containing hyperbranched silicone resin, which is denoted as Resin 6.

[0079] Example 7

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

[0081] (1) 16.8 g of hydroxymethyl phosphonic acid diethyl ester and 24.7 g of isocyanate triethoxysilane were added to a reactor, 0.1 g of iron octoate was added, and the reaction was carried out at 100°C for 24 h;

[0082] (2) 14.8 g of vinyl trimethoxysilane, 12 g of phenylaminomethyl triethoxysilane, and 3.6 g of pure water were added to the system, and the hydrolysis reaction was carried out 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 the reaction was carried out at 100°C for 12 h;

[0084] (4) After the reaction was completed, the solvent and small molecules were removed by vacuum distillation purification treatment to obtain a phosphorus-containing hyperbranched silicone resin, which was denoted as resin 7.

[0085] Table 1

[0086] Resin viscosity (mPa-s) Phosphorous 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 is the viscosity and phosphorus content of the hydrophilic hyperbranched silicone resin with a side group containing a phosphorus group. It can be seen that the viscosity of the hyperbranched resin is low, the modification processing condition is good, in addition, the phosphorus content is controllable, and the phosphorus content can be changed by molecular structure design.

[0088] Figure 1 It can be seen from the physical diagram that the transparent hydrophilic hyperbranched silicone resin with a side group containing phosphorus can be synthesized from examples 1-9.

[0089] Figure 2 The left figure is a physical diagram of the phosphorus-containing hyperbranched silicone prepared in example 1, Figure 2 The right figure is a physical diagram of the phosphorus-containing hyperbranched silicone prepared in example 1 dispersed in water. It can be seen that the prepared phosphorus-containing hyperbranched silicone has good dispersibility in water.

[0090] Figure 3 It can be seen that the particle size distribution of the phosphorus-containing hyperbranched silicone prepared in example 1 dispersed in water, the average particle size is about 25 nm, which shows that the phosphorus-containing hyperbranched silicone can form an emulsion in water.

[0091] Figure 4 It can be seen that the initial thermal decomposition temperature of the phosphorus-containing hyperbranched silicone 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 silicone prepared in example 1 contains C, O, P, Si elements, and the proportion of P element is about 6%.

[0093] Figure 6(Left) is the real picture of unmodified polyurethane emulsion, Figure 6 (Right) is the real picture of phosphorus-containing hyperbranched silicone modified polyurethane emulsion prepared in Example 1, and it can be seen that the modified polyurethane emulsion presents a micro-blue state, indicating that the emulsion has better dispersibility.

[0094] Figure 7 (Left) is the real picture of unmodified polyurethane curing, Figure 7 (Right) is the real picture of phosphorus-containing hyperbranched silicone modified polyurethane curing prepared in Example 1, and 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 is the ignition schematic diagram of unmodified polyurethane, and it can be seen that the unmodified polyurethane is ignited and then continues to burn and has a large amount of falling objects.

[0096] Figure 9 is the ignition schematic diagram of phosphorus-containing hyperbranched silicone modified polyurethane prepared in Example 1, and it can be seen that the ignition is quickly extinguished within 3s, showing good flame retardancy, indicating that the prepared phosphorus-containing hyperbranched silicone has obvious improvement on the flame retardancy of waterborne polyurethane.

[0097] The above only describes the preferred embodiments of the present application, and it should be noted that for ordinary skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A process for the preparation of a hydrophilic hyperbranched silicone resin bearing pendant phosphorus groups, characterized in that: The specific steps are as follows: 1) phosphorus-containing mono- or polyol monomer A and isocyanate-based silane coupling agent monomer B are added to a reactor, the molar ratio of polyol monomer A to isocyanate-based silane coupling agent monomer B is 1:1-3:1, a catalyst is added for reaction, the reaction temperature is 30-150 ℃, and the reaction time is 1-24 h to obtain compound 1; the polyol monomer A is selected from one or more of hydroxymethyl phosphoric acid diethyl ester, hydroxyethyl phosphoric acid dimethyl ester, trimethylol phosphine oxide, pentaerythritol phosphate, N,N-bis(2-hydroxyethyl) aminomethylene phosphonic acid diethyl ester, and [3-[(hydroxymethyl) amino]-3-carbonyl propyl]-phosphonic acid dimethyl ester; the isocyanate-based silane coupling agent monomer B is selected from one or more of 3-isocyanate propyl triethoxysilane and 3-isocyanate propyl trimethoxysilane; and the catalyst is selected from one or more of dibutyl tin dilaurate, stannous octoate, cobalt octoate, lead octoate, iron octoate, zinc naphthenate, and tetrabutyl titanate; 2) silane coupling agent monomer C and water are added to the system for hydrolysis reaction, the hydrolysis reaction temperature is 20-100 ℃, the reaction time is 1-24 h, the molar ratio of compound 1 to silane coupling agent monomer C is 0.01-0.99:0.99:0.01, and the molar ratio of silane coupling agent monomer C to water is 1:0.5-3; the silane coupling agent monomer C is selected from one or more of methyl trimethoxysilane, methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, vinyl trimethoxysilane, γ-glycidyl ether propyl trimethoxysilane, γ-glycidyl ether propyl triethoxysilane, aminopropyl trimethoxysilane, aminopropyl triethoxysilane, phenylaminomethyl triethoxysilane, and phenylaminomethyl trimethoxysilane; and the water is one or more of distilled water, deionized water, and pure water; 3) after hydrolysis, a catalyst and a solvent are added for condensation reaction and growth, the reaction temperature is 20-150 ℃, and the reaction time is 1-36 h; the solvent is selected from one or more of tetrahydrofuran, acetone, dichloromethane, ethyl acetate, toluene, ethanol, N-methyl pyrrolidone, and N,N-dimethylformamide; and the catalyst is selected from one or more of phosphoric acid, hydrochloric acid, benzene sulfonic acid, sodium hydroxide, triethylamine, ammonia, and tetramethylammonium hydroxide; 4) after the reaction is completed, vacuum distillation purification treatment is performed to obtain a hydrophilic hyperbranched organosilicon resin containing a phosphorus group on the side chain; The reaction formula is as follows: ； wherein R1is one of -CH2PO(OCH2CH3)2, -CH2CH2PO(OCH3)2, -CH2PO(CH2OH)2, -CH2CH2N(CH2CH2OH)CH2PO(OCH2CH3)2, -CH2NHCOCH2CH2PO(OCH3)2. R2 is one of -CH2 and -CH2CH3; R is selected from -CH3, -CH2CH3, -CH2CH2CH2NH2, -CH=CH2, , , wherein R in different positions are the same or different; R' is one of -CH2CH2CH2NHCOOCH2PO(CH2OH)2, -CH2CH2CH2NHCOOCH2CH2PO(OCH3)2, -CH2CH2CH2NHCOOCH2PO(OCH2CH3)2, -CH2CH2CH2NHCOOCH2CH2N(CH2CH2OH)CH2PO(OCH2CH3)2, -CH2CH2CH2NHCOOCH2NHCOCH2CH2PO(OCH3)2, one of -CH2CH2CH2NHCOOCH2PO(CH2OH)2, -CH2CH2CH2NHCOOCH2CH2PO(OCH3)2, -CH2CH2CH2NHCOOCH2PO(OCH2CH3)2, -CH2CH2CH2NHCOOCH2CH2N(CH2CH2OH)CH2PO(OCH2CH3)2, -CH2CH2CH2NHCOOCH2NHCOCH2CH2PO(OCH3)2, one of -CH2CH2CH2 2. A hydrophilic hyperbranched organosilicon resin containing a phosphorus group on the side chain prepared by the method of claim 1.

3. Application of the hydrophilic hyperbranched organosilicon resin containing a phosphorus group on the side chain of claim 2 in the preparation of a flame-retardant material.

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