A modified hyperbranched polyether material and a method for preparing the same

Abstract

The application belongs to the technical field of high polymer materials, and particularly relates to a modified hyperbranched polyether material and a preparation method thereof, wherein the modified hyperbranched polyether material is prepared from the following raw materials in parts by weight: 100 parts of hyperbranched polyether, 15-25 parts of a silane modifier and 10-18 parts of a phosphorus hetero ring modifier; the silane modifier comprises gamma-(2,3-epoxypropoxy) propyl trimethoxysilane; and the phosphorus hetero ring modifier comprises at least one of DOPO and DOPO-HQ. The modified hyperbranched polyether material provided by the application can improve the toughness of the material, inhibit crack growth, and make the material have good flame retardant performance.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a modified hyperbranched polyether material and its preparation method. Background Technology

[0002] Epoxy resin is a type of thermosetting polymer material with diverse functions. Due to its good chemical stability, corrosion resistance, heat resistance and low dielectric properties, it is widely used in coatings, adhesives, conductive polymers and high-performance composite materials. However, epoxy resin materials still have the following two problems: (1) After curing, epoxy resin becomes more brittle and less tough, which leads to a decrease in its impact resistance and makes it very easy to generate cracks that propagate rapidly, causing the coating to crack; (2) Epoxy resin has a low oxygen index and is a flammable material. These problems have limited the use of epoxy resin in many fields.

[0003] Hyperbranched polyethers are widely used as toughening agents for epoxy resins. Their highly branched structure and spherical shape allow them to absorb energy through impact deformation, and their abundant terminal groups, such as carboxyl, amino, and epoxy groups, enable them to participate in the curing network, thus increasing the crosslinking density of the epoxy matrix. However, hyperbranched polyethers still suffer from problems as toughening agents, including insufficient interfacial compatibility and susceptibility to chain segment deentanglement or thermal degradation at high temperatures. These issues prevent them from effectively exerting their toughening effect and reduce their crack inhibition capabilities.

[0004] Therefore, how to make materials have both good toughness and good flame retardant properties is an urgent problem to be solved. Summary of the Invention

[0005] In a first aspect, the present invention provides a modified hyperbranched polyether material, prepared from the following raw materials in parts by weight: 100 parts hyperbranched polyether, 15-25 parts silane modifier, and 10-18 parts phosphenanthrene modifier; wherein the silane modifier comprises γ-(2,3-epoxypropoxy)propyltrimethoxysilane; and the phosphenanthrene modifier comprises at least one of DOPO and DOPO-HQ.

[0006] While hyperbranched polyethers can improve the toughness of materials, they suffer from insufficient interfacial compatibility and are prone to deentanglement at high temperatures. Phosphaphenanthrene and its derivatives, while improving flame retardancy, reduce toughness, making materials more susceptible to brittle fracture and increasing the likelihood of crack formation at stress concentration points. Silane modifiers, although enhancing interfacial bonding, lack energy dissipation mechanisms. Energy dissipation mechanisms refer to the ability of a material, when subjected to external forces (such as impact, tension, and vibration), to absorb and convert the applied mechanical energy (i.e., "destructive energy") into other forms of energy through its internal structure, thereby preventing energy concentration at a single point and rapid material failure.

[0007] The inventors discovered that integrating the interfacial reinforcement effect of silane with the rigid flame-retardant structure of phosphaphenanthrene into hyperbranched polyether can construct a crack-inhibiting network that combines rigidity and flexibility: Traditional phosphaphenanthrene flame retardants introduce a rigid aromatic ring structure, which can improve flame retardancy, but it will seriously sacrifice the toughness of the material, making it easier for cracks to initiate at stress concentration points. Hyperbranched polyether can crosslink with silane to form a flexible buffer layer, forming ≡Si-OC≡ covalent bonds and a gradient modulus transition layer. Through molecular-level interfacial bonding, stress concentration points are eliminated, and the embrittlement effect of phosphaphenanthrene is offset, thereby improving the toughness of the material and inhibiting crack growth.

[0008] The inventors discovered that the amounts of silane modifier and phosphenanthrene modifier need to be controlled within a certain range. Too much or too little will affect the performance of the modified hyperbranched polyether material, resulting in poor performance after subsequent compounding with epoxy resin. In some preferred embodiments, the modified hyperbranched polyether material is prepared from the following parts by weight of raw materials: 100 parts hyperbranched polyether, 21-23 parts silane modifier, and 14-16 parts phosphenanthrene modifier.

[0009] Furthermore, the selection of silane modifiers requires special consideration, as not all silane modifiers can react with phosphenanthrene modifiers and hyperbranched polyethers to obtain modified materials with excellent performance. The inventors have found that when using silane modifiers such as 3-(methoxy)propyltrimethoxysilane (KE-561), the resulting materials, when compounded with epoxy resins, exhibit poor performance. In some preferred embodiments, the silane modifier includes γ-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0010] Furthermore, the selection of phosphenanthrene modifiers requires special consideration, as not all phosphenanthrene modifiers can react with silane modifiers and hyperbranched polyethers to obtain modified materials with excellent performance. The inventors have found that when using modifiers such as DOPO-ITA, the resulting materials, when compounded with epoxy resins, exhibit poor performance. In some preferred embodiments, the phosphenanthrene modifier includes at least one of DOPO and DOPO-HQ.

[0011] In some embodiments, the hyperbranched polyether is hyperbranched G3-PEG10k-OH, purchased from Aladdin, catalog number H487754.

[0012] In a second aspect, the present invention provides a method for preparing the above-mentioned modified hyperbranched polyether material, comprising the following steps: simultaneously adding a silane modifier and a phosphenanthrene modifier to a hyperbranched polyether solution to carry out a condensation reaction, and obtaining the modified hyperbranched polyether material after the reaction.

[0013] The inventors discovered that silane modifiers and phosphenanthrene modifiers need to be added simultaneously to hyperbranched polyethers for condensation reactions. If the silane modifier is added first and then the phosphenanthrene modifier, the silane modifier will preferentially react with epoxy groups to form a flexible cross-linked layer, causing the subsequently added phosphenanthrene to be blocked outside the cross-linked network. As a result, the phosphenanthrene accumulates on the resin surface and forms a brittle surface layer after curing.

[0014] In some embodiments, the preparation method of the hyperbranched polyether solution includes the following steps: dissolving the hyperbranched polyether in a polar solvent, adding a catalyst, heating and stirring to obtain the hyperbranched polyether solution.

[0015] In some embodiments, the mass ratio of the hyperbranched polyether to the catalyst is 100:(0.1-1), for example, it can be 100:0.1, 100:0.2, 100:0.4, 100:0.6, 100:0.8, 100:1 or any two of these values.

[0016] In some embodiments, the catalyst comprises dibutyltin dilaurate.

[0017] In some embodiments, the silane modifier is added to the hyperbranched polyether solution in the form of solution A, wherein solution A is a mixed solution of silane modifier and ethanol, and the mass-volume ratio of silane modifier to ethanol is (15-25) g: 50 mL.

[0018] In some embodiments, the phosphenanthrene modifier is added to the hyperbranched polyether solution in the form of solution B, wherein solution B is a mixed solution of phosphenanthrene modifier and tetrahydrofuran (THF) with a mass-to-volume ratio of (10-18) g: 50 mL.

[0019] The inventors discovered that the addition rates of solutions A and B to the hyperbranched polyether solution are best controlled within a certain range. If solution A is added too quickly, the local concentration of the silane modifier in the reaction system will increase sharply, and silane molecules will easily self-condense to form siloxane oligomers, reducing coupling efficiency. If solution B is added too quickly, the local concentration of the phosphenanthrene modifier in the reaction system will be too high, triggering side reactions, reducing grafting efficiency, and also causing uneven grafting, affecting product uniformity.

[0020] In some embodiments, solution A is added to the hyperbranched polyether solution at a rate of 0.5-4.5 mL / min. In some preferred embodiments, solution A is added to the hyperbranched polyether solution at a rate of 1.2-1.5 mL / min.

[0021] In some embodiments, solution B is added to the hyperbranched polyether solution at a rate of 0.5-2.5 mL / min. In some preferred embodiments, solution B is added to the hyperbranched polyether solution at a rate of 1.0-1.3 mL / min.

[0022] In some embodiments, the conditions for the condensation reaction include: a temperature of 70-80°C, an inert gas flow rate of 10-30 mL / min, a stirring speed of 300-700 r / min, a pH of 6-8, and a reaction time of 5-8 h.

[0023] In a third aspect, the present invention provides a composite material, wherein the epoxy resin composite material comprises the above-described modified hyperbranched polyether material.

[0024] In some embodiments, the composite material is an epoxy resin composite material, which further includes epoxy resin and a curing agent.

[0025] In some embodiments, the modified hyperbranched polyether material is added at 1-10% of the epoxy resin mass. In some preferred embodiments, the modified hyperbranched polyether material is added at 4-6% of the epoxy resin mass. In some more preferred embodiments, the modified hyperbranched polyether material is added at 5% of the epoxy resin mass.

[0026] In some embodiments, the curing agent is added at 20-40% of the epoxy resin mass. In some preferred embodiments, the curing agent is added at 30-35% of the epoxy resin mass. In some more preferred embodiments, the curing agent is added at 33% of the epoxy resin mass.

[0027] In some embodiments, the curing agent comprises 4,4'-diaminodiphenyl sulfone (DDS).

[0028] In a fourth aspect, the present invention provides a method for preparing the above-mentioned epoxy resin composite material, comprising the following steps: mixing epoxy resin, curing agent and modified hyperbranched polyether material, and then performing degassing and curing treatment to obtain the epoxy resin composite material.

[0029] In some embodiments, the degassing process is performed in a vacuum degassing chamber: the vacuum level is set to -0.095 MPa, the degassing temperature is 75-85°C, and the degassing time is set to 5-15 minutes, resulting in a degassed epoxy resin solution. In some preferred embodiments, the degassing process is performed in a vacuum degassing chamber: the vacuum level is set to -0.095 MPa, the degassing temperature is 80°C, and the degassing time is set to 10 minutes, resulting in a degassed epoxy resin solution.

[0030] In some embodiments, the curing process is divided into two stages: a first curing stage, where the temperature is increased from 75-85°C at a rate of 1-3°C / min, with a final temperature of 120±2°C and a curing time of 100-140 min; and a second curing stage, where the temperature is increased from 115-125°C at a rate of 1-3°C / min, with a final temperature of 180±2°C. The mold is then allowed to cool naturally to below 60°C in an oven for demolding to obtain the epoxy resin composite material. In some preferred embodiments, the curing process is divided into two stages: a first curing stage, where the temperature is increased from 80°C at a rate of 2°C / min, with a final temperature of 120±2°C and a curing time of 120 minutes; and a second curing stage, where the temperature is increased from 120°C at a rate of 2°C / min, with a final temperature of 180±2°C. The mold is then allowed to cool naturally to below 60°C in an oven for demolding to obtain the epoxy resin composite material.

[0031] Compared with the prior art, the present invention has the following beneficial effects: The modified hyperbranched polyether material provided by this invention can eliminate stress concentration caused by interface defects, effectively improve the toughness of the material and inhibit crack growth, while giving the material good flame retardant properties, effectively solving the contradiction between flame retardant properties and toughening properties, and has good application prospects. Detailed Implementation

[0032] The following detailed embodiments further illustrate the content of the present invention. These embodiments do not constitute a limitation on the scope of protection of the present invention. Non-essential modifications and adjustments made by others based on the concept of the present invention still fall within the scope of protection of the present invention. The raw materials, reagents, or devices used in the embodiments are all available from conventional commercial sources or can be obtained through existing technical methods. Unless otherwise specified, the experimental or testing methods are conventional methods in the art.

[0033] The materials and sources used in the embodiments and comparative examples are shown in Table 1.

[0034] Table 1 Preparation of modified hyperbranched polyether crack-inhibiting materials Example 1 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0035] S2. Solution Preparation and Condensation Reaction: 22g of γ-GPS was dissolved in 50 mL of anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A. 15g of DOPO-HQ was dissolved in 50 mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively, and added dropwise simultaneously. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. The temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction, which lasted for 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 87%.

[0036] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0037] Example 2 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0038] S2. Solution Preparation and Condensation Reaction: 18g of γ-GPS was dissolved in 50 mL of anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A. 18g of DOPO-HQ was dissolved in 50 mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively, and added dropwise simultaneously. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. During the dropwise addition, the temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction, which lasted for 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Once the two characteristic peaks disappear, heating should be stopped immediately, and the temperature should be lowered to 25°C in an ice-water bath. The conversion rate is 88%.

[0039] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0040] The only difference between Example 2 and Example 1 is that the amount of γ-GPS and DOPO-HQ added in step S2 is changed.

[0041] Example 3 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0042] S2. Solution Preparation and Condensation Reaction: 25g of γ-GPS was dissolved in 50mL of anhydrous ethanol by ultrasonication at 40kHz for 10 minutes to obtain solution A. 10g of DOPO-HQ was dissolved in 50mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively, and added dropwise simultaneously. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. During the dropwise addition, the temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction, which lasted for 7 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 91%.

[0043] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0044] The only difference between Example 3 and Example 1 is that the amount of γ-GPS and DOPO-HQ added in step S2 is changed.

[0045] Example 4 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0046] S2. Solution Preparation and Condensation Reaction: 15g of γ-GPS was dissolved in 50mL of anhydrous ethanol by ultrasonication at 40kHz for 10 minutes to obtain solution A. 12g of DOPO-HQ was dissolved in 50mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively, and added dropwise simultaneously. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. During the dropwise addition, the temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction, which lasted for 5 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 86%.

[0047] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0048] The only difference between Example 4 and Example 1 is that the amount of γ-GPS and DOPO-HQ added in step S2 is changed.

[0049] Example 5 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0050] S2. Solution Preparation and Condensation Reaction: 22g of γ-GPS was dissolved in 50 mL of anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A. 15g of DOPO was dissolved in 50 mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively, and added dropwise simultaneously. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. The temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction, which lasted for 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 84%.

[0051] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0052] The only difference between Example 5 and Example 1 is that DOPO-HQ in step S2 is replaced with DOPO.

[0053] Comparative Example 1 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0054] S2. Solution Preparation and Condensation Reaction: 22g of γ-GPS was dissolved in 50 mL of anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A. 15g of DOPO-ITA was dissolved in 50 mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively, and added dropwise simultaneously. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. During the dropwise addition, the temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction, which lasted for 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 52%.

[0055] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0056] The only difference between Comparative Example 1 and Example 1 is that DOPO-HQ in step S2 is replaced with DOPO-ITA.

[0057] Comparative Example 2 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0058] S2. Solution Preparation and Condensation Reaction: 22g of γ-GPS was dissolved in 50 mL of anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A. 30g of DOPO-HQ was dissolved in 50 mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively, and added dropwise simultaneously. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. The temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction, which lasted for 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 34%.

[0059] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0060] The only difference between Comparative Example 2 and Example 1 is that the amount of DOPO-HQ added in step S2 is changed.

[0061] Comparative Example 3 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0062] S2. Solution Preparation and Condensation Reaction: 22g of γ-GPS was dissolved in 50 mL of anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A. 5g of DOPO-HQ was dissolved in 50 mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively, and added dropwise simultaneously. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. The temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction, which lasted for 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 36%.

[0063] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0064] The only difference between Comparative Example 3 and Example 1 is that the amount of DOPO-HQ added in step S2 is changed.

[0065] Comparative Example 4 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0066] S2. Solution Preparation and Condensation Reaction: 22g KH-561 was dissolved in 50 mL anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A. 15g DOPO-HQ was dissolved in 50 mL THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively, and added dropwise simultaneously. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. The temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction, which lasted for 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 56%.

[0067] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0068] The only difference between Comparative Example 4 and Example 1 is that γ-GPS in step S2 is replaced with KH-561.

[0069] Comparative Example 5 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0070] S2. Solution Preparation and Condensation Reaction: 40g of γ-GPS was dissolved in 50mL of anhydrous ethanol by ultrasonication at 40kHz for 10 minutes to obtain solution A. 15g of DOPO-HQ was dissolved in 50mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively, and added dropwise simultaneously. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. During the dropwise addition, the temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction, which lasted for 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 51%.

[0071] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0072] The only difference between Comparative Example 5 and Example 1 is that the amount of γ-GPS added in step S2 is changed.

[0073] Comparative Example 6 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0074] S2. Solution Preparation and Condensation Reaction: 5g of γ-GPS was dissolved in 50 mL of anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A; 15g of DOPO-HQ was dissolved in 50 mL of THF in a 60°C water bath to obtain solution B. The remaining steps and component amounts were exactly the same as in Example 1. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively, and added dropwise simultaneously. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. During the dropwise addition, the temperature was maintained at 75±1°C, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the dropwise addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction, and the reaction time was 6 hours. Every 30 minutes during the reaction, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 22%.

[0075] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0076] The only difference between Comparative Example 6 and Example 1 is that the amount of γ-GPS added in step S2 is changed.

[0077] Comparative Example 7 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0078] S2. Solution Preparation and Condensation Reaction: 22g of γ-GPS was dissolved in 50 mL of anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A. 15g of DOPO-HQ was dissolved in 50 mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively. The dropping rate in channel 1 was set to 1.5 mL / min, and the dropping rate in channel 2 was set to 3 mL / min. The temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction. The reaction time was 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 23%.

[0079] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0080] The only difference between Comparative Example 7 and Example 1 is that the drip rate of channel 2 in step S2 is changed.

[0081] Comparative Example 8 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0082] S2. Solution Preparation and Condensation Reaction: 22g of γ-GPS was dissolved in 50 mL of anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A. 15g of DOPO-HQ was dissolved in 50 mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively. The dropping rate in channel 1 was set to 5 mL / min, and the dropping rate in channel 2 was set to 3 mL / min. The temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction. The reaction time was 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 26%.

[0083] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0084] The only difference between Comparative Example 8 and Example 1 is that the drip rate of channel 1 in step S2 is changed.

[0085] Comparative Example 9 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0086] S2. Solution Preparation and Condensation Reaction: 22g of γ-GPS was dissolved in 50 mL of anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A. 15g of DOPO-HQ was dissolved in 50 mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively. Solution A was added dropwise first, followed by solution B. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. During the dropwise addition, the temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the dropwise addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction. The reaction time was 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Once the two characteristic peaks disappear, heating should be stopped immediately, and the temperature should be lowered to 25°C in an ice-water bath. The conversion rate is 20%.

[0087] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0088] The only difference between Comparative Example 9 and Example 1 is that in step S2, solution A and solution B are not added at the same time. Specifically, solution A is added first, followed by solution B.

[0089] Comparative Example 10 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0090] S2. Solution Preparation and Condensation Reaction: 22g of γ-GPS was dissolved in 50 mL of anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A. 15g of DOPO-HQ was dissolved in 50 mL of THF in a 60℃ water bath to obtain solution B. Solutions A and B were placed in channels 1 and 2 of a dual-channel constant flow pump, respectively. Solution B was added dropwise first, followed by solution A. The drop rate in channel 1 was set to 1.5 mL / min, and the drop rate in channel 2 was set to 1.2 mL / min. During the dropwise addition, the temperature was maintained at 75±1℃, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise during the dropwise addition to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction. The reaction time was 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 18%.

[0091] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0092] The only difference between Comparative Example 10 and Example 1 is that in step S2, solution A and solution B are not added at the same time. Specifically, solution B is added first, followed by solution A.

[0093] Comparative Example 11 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0094] S2. Solution Preparation and Condensation Reaction: 22 g of γ-GPS was dissolved in 50 mL of anhydrous ethanol by ultrasonication at 40 kHz for 10 minutes to obtain solution A. Solution A was placed in channel 1 of a dual-channel constant flow pump, with a dropping rate of 1.5 mL / min. During the dropping process, the temperature was maintained at 75 ± 1 °C, the nitrogen flow rate was maintained at 20 mL / min, and the stirring speed was maintained at 500 rpm. Triethylamine was added dropwise to adjust the pH to 7.0 ± 0.1. The pH was measured every 30 minutes during the reaction. The reaction time was 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 16%.

[0095] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0096] The only difference between Comparative Example 11 and Example 1 is that solution B is not added in step S2 (i.e., DOPO-HQ is not grafted).

[0097] Comparative Example 12 A modified hyperbranched polyether material is prepared by the following steps: S1. Activation of hyperbranched polyether core: Add 100g of G3 generation hyperbranched polyether (hyperbranched G3-PEG10k-OH, Aladdin) and 300 mL of anhydrous DMF to a four-necked flask; purge with nitrogen at a flow rate of 50 mL / min for 10 minutes; add 0.6g of dibutyltin dilaurate and stir in a heated magnetic stirrer at a temperature of 70℃ and a speed of 300 r / min until the system is homogeneous and transparent.

[0098] S2. Solution Preparation and Condensation Reaction: 15g of DOPO-HQ was dissolved in 50mL of THF in a 60℃ water bath to obtain solution B. Solution B was placed in channel 2 of a dual-channel constant flow pump, with a dropping rate of 1.2 mL / min. During the dropping process, the temperature was maintained at 75±1℃, the nitrogen flow rate at 20 mL / min, and the stirring speed at 500 rpm. Triethylamine was added dropwise to maintain the pH at 7.0±0.1. The pH was measured every 30 minutes during the reaction. The reaction time was 6 hours. Every 30 minutes, a small amount of the reaction solution was placed on an ATR crystal and monitored at 2280 cm⁻¹ using FTIR. -1 (Si-OH) and 3540 cm -1 (P-OH) characteristic peaks. Heating was stopped immediately after the two characteristic peaks disappeared, and the temperature was lowered to 25°C in an ice-water bath. The conversion rate was 32%.

[0099] S3. Purification: The reaction solution was transferred to a regenerated cellulose dialysis bag and dialyzed in deionized water for 48 hours, changing the water every 8 hours, until the conductivity of the dialysate was ≤5 μS / cm and the dialysate had no silane odor. The reaction solution was then spray-dried, with the feed rate controlled at 10 mL / min and the inlet and outlet temperatures at 180℃ and 80℃, respectively. The resulting pale yellow powder was the modified hyperbranched polyether material.

[0100] The only difference between Comparative Example 12 and Example 1 is that solution A is not added in step S2 (i.e., γ-GPS is not grafted).

[0101] Application Example 1: Preparation of Epoxy Resin Composite Material I The modified hyperbranched polyether materials prepared in the examples and comparative examples were used to prepare epoxy resin composite material I. The preparation steps are as follows: (1) Premixing: 100g of epoxy resin (Dow DER732Flex) preheated to 80℃ was added to the mixing tank of a high-speed disperser, followed by 5g of the modified hyperbranched polyether material prepared in the examples or comparative examples. The revolution speed was set to 2000 rpm and the rotation speed to 800 rpm. The tank jacket was circulated and the temperature was controlled at 80±2℃ for 30 minutes. Samples were taken every 5 minutes and the viscosity was tested. The endpoint viscosity was required to be ≤350cP (25℃).

[0102] (2) Adding curing agent and degassing: Weigh 33g of 4,4'-diaminodiphenyl sulfone (DDS) powder, add DDS powder to the sample and stir manually to avoid powder flying, then put it into a vacuum degassing box, set the vacuum degree to -0.095MPa, the degassing temperature to 80℃, and the degassing time to 10 minutes to obtain the degassed epoxy resin solution.

[0103] (3) Curing process: The degassed epoxy resin solution is injected into the anodized aluminum mold, ensuring that the liquid surface is flat and free of bubbles. It is placed in a programmable temperature-controlled oven for curing, which is divided into two stages: the first stage of curing is to increase the temperature from 80°C at a rate of 2°C / min, and the final temperature is set to 120±2°C, with a curing time of 120 minutes; the second stage of curing is to increase the temperature from 120°C at a rate of 2°C / min, and the final temperature is set to 180±2°C; finally, the mold is allowed to cool naturally to below 60°C in the oven for demolding, to obtain the epoxy resin composite material I.

[0104] Test Example 1: Performance Testing of Epoxy Resin Composite Material I (1) Fracture toughness test The epoxy resin composite material I prepared in the examples and comparative examples was cut into pieces measuring 60×12×6 mm. 3 A cuboid (dimensional tolerance ±0.1 mm) was cut with a diamond wire saw (0.1 mm wire diameter) to create a single-sided notch in the middle of the specimen. The notch length was 2.4 mm, and the notch tip radius was ≤5 μm. A three-point bending test was performed on the specimen, with a span S of 48 mm, a loading rate of 1 mm / min, an ambient temperature of 23 ± 2 °C, and an ambient relative humidity of 50 ± 5% RH. The stress intensity factor (K) at the start of unstable crack propagation in the specimen was calculated according to formula (1). IC ), K IC K is a mechanical property index of a material's resistance to unstable crack propagation. IC A higher value indicates that cracks are less likely to propagate and the material is less likely to fracture brittlely. The test results are shown in Table 2.

[0105] Formula (1) is shown below: In formula (1), P max Where α is the maximum load, B is the specimen thickness, W is the specimen width, and f(α / W) is the specimen geometry factor.

[0106] (2) Crack propagation rate test The epoxy resin composite material I prepared in the examples and comparative examples was used to prepare compact tensile specimens with a width of 50 mm and a thickness of 6 mm, and fatigue cracks were pre-induced, where ΔK is the stress intensity factor range of 0.5 MPa·(m²). 1 / 2 The stress ratio is 0.1 (Pmin / Pmax), and the loading frequency is 10Hz (sine wave), where Pmax is the maximum load during fatigue cyclic loading and Pmin is the minimum load during fatigue cyclic loading.

[0107] The machine is stopped and the sample is removed after every 1000 cycles. The crack length a is observed and measured using a 40x optical microscope. The crack propagation rate is calculated according to Paris's formula (2), which is shown below: In formula (2), m is the Paris exponent, C is the material constant, da is the crack propagation rate, representing the increase in crack length per loading cycle, in mm / cycle; dN is the change in the number of fatigue loading cycles; ΔK is the stress intensity factor range, in MPa·m. 1 / 2 , which represents the magnitude of the change in the stress field at the crack tip under cyclic loading.

[0108] A higher crack propagation rate means that the material is more sensitive to fatigue cracks, is prone to rapid propagation, and may lead to early fracture.

[0109] The test results are shown in Table 2.

[0110] (3) Crack deflection angle test The epoxy resin composite material I prepared in the examples and comparative examples was subjected to liquid nitrogen brittle fracture. The fracture surface was then sputter-coated with gold to form a 5nm Au / Pd layer. The crack deflection angle was observed using a scanning electron microscope with an accelerating voltage of 5kV and a working distance of 6mm. Ten measurement points were selected along the crack propagation path, and the angle between the line connecting adjacent points and the horizontal axis was calculated using ImageJ software. The average value was then taken. A larger crack deflection angle indicates that the material is more sensitive to fatigue cracks, is prone to rapid propagation, and may lead to early fracture.

[0111] The test results are shown in Table 2.

[0112] Table 2 Application Example 2: Preparation of Epoxy Resin Composite Material II (1) Take 6g of the modified hyperbranched polyether material prepared in the example or comparative example, add 40g of butyl acetate and ball mill and disperse (zirconia beads φ0.5 mm, 300 rpm, 2 h) until the particle size D50≤5 μm to obtain the modifier dispersion.

[0113] (2) Preparation of component A: Take 100g of polyether polyol (VORANOL 2120, Dow Chemical), 46g of modifier dispersion and 0.5g of leveling agent (BYK-333). Preheat the polyether polyol to 50±2℃ to reduce its viscosity. Then add the modifier dispersion and leveling agent. Place the mixture in a mixer and stir for 15 minutes at a revolution speed of 2000 rpm and a rotation speed of 800 rpm. Perform vacuum degassing on it. The vacuum degree is set to -0.095MPa, the degassing temperature is 50℃, and the degassing time is set to 10 minutes to obtain the polyol phase containing the modifier (i.e., component A).

[0114] (3) Preparation of component B: Take 40g of polyisocyanate and preheat it at 40℃ for 30min.

[0115] (4) Pour component B into component A to obtain a mixture. Place the mixture in a mixer and stir at 800 rpm for 2 minutes until homogeneous. Then perform vacuum degassing with a vacuum degree of -0.095 MPa, a degassing temperature of 25°C, and a degassing time of 5 minutes.

[0116] (5) Prepare glass fiber reinforced epoxy board (Piedmont Plastics, G10 / FR-4) (100×100×3mm) 3 Using the epoxy resin composite material II prepared above as the substrate, the substrate was sandblasted with 80-mesh fused alumina sand to achieve a surface roughness of Ra = 3.2 ± 0.2 μm. The spraying process was carried out using a 1.3 mm nozzle diameter spray gun, with a spraying pressure of 0.5 MPa, a gun distance of 20 ± 2 cm, a gun travel speed of 30 cm / s, and a target film thickness of 150 ± 10 μm. The substrate was left to stand at 25°C for 72 hours until no trace was left when lightly pressed with a finger. Forced curing was performed using a forced-air oven with a heating rate of 2°C / min, reaching 80°C and maintaining the temperature for 2 hours to obtain epoxy resin composite material II.

[0117] Test Example 2: Performance Testing of Epoxy Resin Composite Material II (1) Salt spray resistance test Salt spray test solution: 5.0±0.5 wt% NaCl salt solution, pH value 6.5-7.2, chamber temperature 35±2℃, continuous spraying, salt spray deposition rate 1.5 mL / 80 cm²·h.

[0118] Salt spray test method: A diamond scriber is used to make cross-shaped scratches on the surface of the sample, with a scratch length of 20 mm and a depth to the substrate. Samples from the salt spray aging test are taken and cleaned every 240 hours. The crack length at the scratch tip is observed under a microscope, and the crack propagation rate is calculated according to formula (3), as shown below: Where da is the crack propagation rate, dN is the change in the number of fatigue load cycles, Δa is the increment of crack length, and Δt is the time increment of crack length.

[0119] The test results are shown in Table 3.

[0120] (2) Impact resistance test (room temperature drop hammer impact test) The coating was placed at room temperature and impacted with a 20mm diameter (hemispherical) punch at an energy of 15J (mass 6kg, height 255mm) and a velocity of 2.2m / s. After impact, the crack area in the coating was detected using C-scan ultrasonic testing. The test results are shown in Table 3.

[0121] (3) Heat aging resistance test The coating was placed in an oven at 80±3℃ for 2000 hours. After heat aging, the coating underwent fracture toughness testing using the four-point bend test method. Coating adhesion was assessed using the cross-cut adhesion test (ISO 2409), with grades ranging from 0 to 5. Higher grades indicate better adhesion. The test results are shown in Table 3.

[0122] Table 3 The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A modified hyperbranched polyether material, characterized in that, It is prepared from the following raw materials in parts by weight: 100 parts of hyperbranched polyether, 15-25 parts of silane modifier and 10-18 parts of phosphaphenanthrene modifier; The silane modifier includes γ-(2,3-epoxypropoxy)propyltrimethoxysilane; The phosphorophenanthrene modifier includes at least one of DOPO and DOPO-HQ.

2. The modified hyperbranched polyether material as described in claim 1, characterized in that, The modified hyperbranched polyether material is prepared from the following raw materials in parts by weight: 100 parts hyperbranched polyether, 21-23 parts silane modifier, and 14-16 parts phosphaphenanthrene modifier.

3. A method for preparing the modified hyperbranched polyether material as described in any one of claims 1-2, characterized in that, The process includes the following steps: adding silane modifier and phosphenanthrene modifier simultaneously to a hyperbranched polyether solution to carry out a condensation reaction, and obtaining the modified hyperbranched polyether material after the reaction.

4. The preparation method according to claim 3, characterized in that, The preparation method of the hyperbranched polyether solution includes the following steps: dissolving the hyperbranched polyether in a polar solvent, adding a catalyst, and heating and stirring to obtain the hyperbranched polyether solution; the mass ratio of the hyperbranched polyether to the catalyst is 100:(0.1-1); the catalyst includes dibutyltin dilaurate.

5. The preparation method according to claim 3, characterized in that, The silane modifier is added to the hyperbranched polyether solution in the form of solution A, which is a mixed solution of silane modifier and ethanol, and the rate at which solution A is added to the hyperbranched polyether solution is 0.5-4.5 mL / min.

6. The preparation method according to claim 5, characterized in that, The rate at which solution A is added to the hyperbranched polyether solution is 1.2-1.5 mL / min.

7. The preparation method according to claim 3, characterized in that, The phosphenanthrene modifier is added to the hyperbranched polyether solution in the form of solution B, which is a mixed solution of the phosphenanthrene modifier and tetrahydrofuran. The solution B is added to the hyperbranched polyether solution at a rate of 0.5-2.5 mL / min.

8. The preparation method according to claim 7, characterized in that, The solution B is added to the hyperbranched polyether solution at a rate of 1.0-1.3 mL / min.

9. The preparation method according to claim 3, characterized in that, The conditions for the condensation reaction include: a temperature of 70-80℃, an inert gas flow rate of 10-30 mL / min, a stirring speed of 300-700 r / min, a pH of 6-8, and a reaction time of 5-8 h.

10. A composite material, characterized in that, The composite material includes the modified hyperbranched polyether material as described in claim 1.

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