A nano-structured synergistic toughening high impact polymer modifier and a method for preparing the same

Abstract

The application discloses a nano-structure synergistic toughening high-impact polymer modifier and a preparation method thereof. The modifier comprises 5-15 parts of terminal glycidyl hyperbranched triazine-polyether ester oligomer, 82-94 parts of fibrillatable polymer phase and 1-3 parts of nano-morphology regulator. The terminal glycidyl hyperbranched triazine-polyether ester oligomer is prepared by the following steps: reacting cyanuric chloride with p-hydroxybenzoic acid to obtain a triazine core triacid, esterifying polytetrahydrofuran diol and 1,4-butanediol to carry out polycondensation, and finally performing glycidylation reaction. The application realizes the unification of high rigidity, high toughness and high structural stability by the interface bonding effect of the hyperbranched oligomer, the fibrous dispersion toughening of the fibrillatable polymer phase and the morphology stabilizing effect of the nano-morphology regulator, and the stable fibrous dispersion phase structure is constructed by the three, so that the high-impact modification of engineering plastics such as polybutylene terephthalate, polyamide and polycarbonate can be widely applied.

Description

Technical Field

[0001] This invention relates to the field of polymer modifier technology, and in particular to a high-impact polymer modifier with synergistic toughening by nanostructures and its preparation method. Background Technology

[0002] Polymer materials are widely used in the automotive, electronics, and aerospace industries due to their advantages such as light weight, ease of processing, and low cost. However, most engineering plastics (such as polybutylene terephthalate, polyethylene terephthalate, polyamide, and polycarbonate) are brittle at room temperature or low temperatures and have low notched impact strength, which severely limits their application in high-end structural components. Therefore, toughening modification of these polymers has become a key technical means to expand their application range.

[0003] Currently, polymer toughening modification mainly employs elastomer toughening technology, which involves adding rubber-like elastomers (such as core-shell rubber, polyolefin elastomers, thermoplastic polyester elastomers, etc.) to a brittle polymer matrix. The elastomer particles induce shear yielding or creasing in the matrix, absorbing impact energy and thus improving the material's toughness. However, traditional elastomer toughening has significant drawbacks: on the one hand, the addition of elastomers significantly reduces the material's modulus and strength, making it difficult to balance rigidity and toughness; on the other hand, the dispersion morphology of the elastomer in the matrix is ​​difficult to control precisely, and excessively large or unevenly distributed dispersed phases can affect toughening efficiency.

[0004] Hyperbranched polymers exhibit unique advantages in polymer blending modification due to their distinctive dendritic structure, abundant terminal functional groups, and excellent interfacial activity. However, research on synergistically constructing an integrated toughening system of "interfacial reaction-morphology regulation-structural stability" by combining them with fibrillable polymer phases and nano-morphology modifiers is still lacking. Therefore, inducing the formation of a stable fibrous dispersed phase in the matrix by leveraging the interfacial reactivity of hyperbranched oligomers, the deformability of fibrillable polymer phases, and the morphology stabilizing effect of nano-morphology modifiers, thereby achieving synergistic optimization of rigidity maintenance and toughness enhancement, is a technical challenge that urgently needs to be addressed. Summary of the Invention

[0005] To address the aforementioned problems, this invention proposes a high-impact polymer modifier with synergistic toughening through nanostructures and its preparation method. Through the ternary synergy of terminal glycidyl-terminated hyperbranched triazine-polyether ester oligomer, fibrillable polymer phase, and nanomorphology modifier, a stable fibrous dispersed phase is induced to form in the polymer matrix, achieving synergistic toughening through nanostructures. This effectively solves the problems of difficulty in balancing rigidity and toughness and difficulty in controlling the morphology of the dispersed phase in existing toughening technologies.

[0006] This invention can be achieved through the following technical solutions:

[0007] A high-impact polymer modifier with synergistic toughening by nanostructure, the polymer modifier comprising the following components in parts by weight: 5-15 parts of terminal glycidyl hyperbranched triazine-polyether ester oligomer, 82-94 parts of fiberizable polymer phase, and 1-3 parts of nanomorphology modifier.

[0008] The preparation method of the terminal glycidyl hyperbranched triazine-polyether ester oligomer is as follows: Cyanurium chloride, p-hydroxybenzoic acid, and a base are added to an acetone / water mixed solvent in a molar ratio of 1:(3.0-3.6):(3.0-6.0). The reaction is carried out under stepwise temperature control. After the reaction is completed, the pH is adjusted to 2-4, a solid is precipitated and purified to obtain 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine. Triazine nucleotide monomer, polytetrahydrofuran glycol, and 1,4-butanediol are added to N,N-dimethylformamide in a molar ratio of 1:(0.3-1.2)(0.2-1.5). An esterification polycondensation reaction is carried out in the presence of a catalyst to obtain a hyperbranched triazine-polyether ester intermediate. The intermediate is reacted with epichlorohydrin to carry out a glycidylation reaction to obtain the terminal glycidyl hyperbranched triazine-polyether ester oligomer.

[0009] Preferably, the fibrillable polymer phase is a thermoplastic polyester elastomer or a thermoplastic polyurethane.

[0010] Preferably, the nanomorphology modifier is aminosilane-modified nano-silica particles with a primary particle size of 10-50 nm.

[0011] Preferably, the stepwise temperature control specifically involves: conducting the first-step substitution reaction at 0-10℃ for 1-4 hours, then raising the temperature to 35-60℃ for 2-8 hours to complete the subsequent substitution reaction; the esterification polycondensation reaction is carried out at a temperature of 140-180℃ for 4-12 hours, and the catalyst is selected from at least one of p-toluenesulfonic acid, titanate catalyst, or tin-based catalyst; the glycidylation reaction is carried out at a temperature of 40-90℃ for 2-10 hours.

[0012] Preferably, in the glycidylation reaction, the molar ratio of carboxyl group, epichlorohydrin and base in the hyperbranched triazine-polyether ester intermediate is 1:(2-10):(1-3).

[0013] The preparation method of the above-mentioned high impact-resistant polymer modifier with synergistic toughening of nanostructure is as follows: First, the terminal glycidyl group hyperbranched triazine-polyether ester oligomer, the fiberizable polymer phase and the nano morphology modifier are premixed, and then added to a twin-screw extruder for melt blending and granulation to obtain the polymer modifier; wherein, the screw speed of the twin-screw extruder is 150-500 rpm and the temperature is 190-260℃.

[0014] The beneficial effects of this invention are:

[0015] This invention constructs an integrated toughening system of "interfacial reaction-morphology regulation-structural stability" through the synergistic effect of a ternary structure consisting of a glycidyl-terminated hyperbranched triazine-polyether ester oligomer, a fibrillable polymer phase, and a nano-morphology modifier. The glycidyl-terminated hyperbranched triazine-polyether ester oligomer contains multiple glycidyl groups, which can react with terminal carboxyl and hydroxyl groups in the polymer matrix during melt blending to form interfacial chemical bonds, significantly improving the interfacial bonding strength between the modifier and the matrix. The fibrillable polymer phase forms a fibrous dispersion in situ under shear field, achieving efficient toughening through fiber bridging and stress transfer mechanisms. The nano-morphology modifier is uniformly dispersed in the system, and through hydrogen chemical bonds formed between its surface amino groups and the hyperbranched oligomer and fibrillable polymer phase, it effectively inhibits the shrinkage and co-agglomeration of the fibrous dispersion, ensuring the stability of the fiber morphology. The synergistic effect of these three components realizes a nanostructure-based synergistic toughening mechanism. The polymer modifier prepared in this invention, when added to polybutylene terephthalate (PBT) matrix resin, can form a stable fibrous dispersed phase structure with a notched impact strength of 24.8 kJ / m. 2 Meanwhile, the tensile strength retention rate exceeds 95%, the glass transition temperature increases by 8-10℃, and the high-temperature energy storage modulus remains excellent. Attached Figure Description

[0016] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings:

[0017] Figure 1 The mechanical properties of the spline;

[0018] Figure 2 is the glass transition temperature of the spline. Detailed Implementation

[0019] The following provides a detailed description of the embodiments of the present invention: These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions.

[0020] Example 1: A method for preparing a high-impact polymer modifier with synergistic toughening through nanostructures, comprising the following steps:

[0021] Step 1: Add 1 mol of cyanuric chloride, 3 mol of p-hydroxybenzoic acid and 3 mol of sodium hydroxide to 2 L of acetone / water mixed solvent (volume ratio 1:1), react at 0℃ for 4 h, then raise the temperature to 35℃ and react for 8 h. After the reaction is completed, adjust the pH to 2 with hydrochloric acid, and a white solid precipitates. After filtration, washing with water and recrystallization with ethanol, 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine is obtained.

[0022] Step 2: Add 1 mol of triazine nucleotide monomer, 0.3 mol of polytetrahydrofuran glycol and 0.2 mol of 1,4-butanediol to 2 L of N,N-dimethylformamide, add p-toluenesulfonic acid as a catalyst, and react at 140 °C for 12 h. After the reaction is completed, remove the solvent by vacuum distillation to obtain hyperbranched triazine-polyether ester intermediate.

[0023] Step 3: Add 1 mol of the above hyperbranched triazine-polyether ester intermediate (based on carboxyl groups), 2 mol of epichlorohydrin and 1 mol of sodium hydroxide to the reaction vessel and react at 40°C for 10 h. After the reaction is completed, filter to remove salts and remove excess epichlorohydrin by vacuum distillation to obtain terminal glycidyl hyperbranched triazine-polyether ester oligomer.

[0024] Step 4: Weigh 5 parts of terminal glycidyl hyperbranched triazine-polyether ester oligomer, 94 parts of polyether thermoplastic polyurethane, and 1 part of aminosilane-modified nano silica particles (10 nm primary particle size). Premix them in a mixer for 5 min. Add the premix to a twin-screw extruder for melt blending (screw speed 150 rpm, zone temperatures 190℃, 210℃, 240℃, 260℃, 245℃) and extrude to granulate, to obtain a high-impact polymer modifier with synergistic toughening of nanostructure.

[0025] Example 2: A method for preparing a high-impact polymer modifier with synergistic toughening through nanostructures, comprising the following steps:

[0026] Step 1: Add 1 mol cyanuric chloride, 3.2 mol p-hydroxybenzoic acid and 4 mol sodium hydroxide to 2 L acetone / water mixed solvent (volume ratio 1:1), react at 5℃ for 2.5 h, then raise the temperature to 47.5℃ and react for 5 h. After the reaction is completed, adjust the pH to 3 with hydrochloric acid, and a white solid precipitates. After filtration, washing with water and recrystallization with ethanol, 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine is obtained.

[0027] Step 2: Add 1 mol of triazine nucleotide monomer, 0.75 mol of polytetrahydrofuran glycol and 0.85 mol of 1,4-butanediol to 2 L of N,N-dimethylformamide, add p-toluenesulfonic acid as a catalyst, and react at 160 °C for 8 h. After the reaction is completed, remove the solvent by vacuum distillation to obtain hyperbranched triazine-polyether ester intermediate.

[0028] Step 3: Add 1 mol of the above hyperbranched triazine-polyether ester intermediate (based on carboxyl groups), 6 mol of epichlorohydrin and 2 mol of sodium hydroxide to the reactor and react at 65°C for 6 h. After the reaction is completed, filter to remove salts and remove excess epichlorohydrin by vacuum distillation to obtain terminal glycidyl hyperbranched triazine-polyether ester oligomer.

[0029] Step 4: Weigh 10 parts of terminal glycidyl hyperbranched triazine-polyether ester oligomer, 88 parts of polyether thermoplastic polyurethane, and 2 parts of aminosilane-modified nano silica particles (30nm primary particle size). Premix them in a mixer for 5 minutes. Add the premix to a twin-screw extruder for melt blending (screw speed 325rpm, zone temperatures 190℃, 210℃, 240℃, 260℃, 245℃) and extrude to granulate, to obtain a high-impact polymer modifier with synergistic toughening of nanostructure.

[0030] Example 3: A method for preparing a high-impact polymer modifier with synergistic toughening through nanostructures, comprising the following steps:

[0031] Step 1: Add 1 mol of cyanuric chloride, 3.4 mol of p-hydroxybenzoic acid and 5 mol of sodium hydroxide to 2 L of acetone / water mixed solvent (volume ratio 1:1), react at 10℃ for 1 h, then raise the temperature to 60℃ and react for 2 h. After the reaction is completed, adjust the pH to 4 with hydrochloric acid, and a white solid precipitates. After filtration, washing with water and recrystallization with ethanol, 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine is obtained.

[0032] Step 2: Add 1 mol of triazine nucleotide monomer, 1.2 mol of polytetrahydrofuran diol and 1.5 mol of 1,4-butanediol to 2 L of N,N-dimethylformamide, add p-toluenesulfonic acid as a catalyst, and react at 180 °C for 4 h. After the reaction is completed, remove the solvent by vacuum distillation to obtain hyperbranched triazine-polyether ester intermediate.

[0033] Step 3: Add 1 mol of the above hyperbranched triazine-polyether ester intermediate (based on carboxyl groups), 10 mol of epichlorohydrin and 3 mol of sodium hydroxide to the reaction vessel, and react at 90°C for 2 h. After the reaction is completed, filter to remove salts, and remove excess epichlorohydrin by vacuum distillation to obtain terminal glycidyl hyperbranched triazine-polyether ester oligomer.

[0034] Step 4: Weigh 15 parts of terminal glycidyl hyperbranched triazine-polyether ester oligomer, 82 parts of polyether thermoplastic polyurethane, and 3 parts of aminosilane modified nano silica particles (50 nm primary particle size). Premix them in a mixer for 5 min. Add the premix to a twin-screw extruder for melt blending (screw speed 500 rpm, zone temperatures 190℃, 210℃, 240℃, 260℃, 245℃) and extrude to granulate, to obtain a high-impact polymer modifier with synergistic toughening of nanostructure.

[0035] Example 4: A method for preparing a high-impact polymer modifier with synergistic toughening through nanostructures, comprising the following steps:

[0036] Step 1: Add 1 mol of cyanuric chloride, 3.6 mol of p-hydroxybenzoic acid and 6 mol of sodium hydroxide to 2 L of acetone / water mixed solvent (volume ratio 1:1), react at 10℃ for 1 h, then raise the temperature to 60℃ and react for 2 h. After the reaction is completed, adjust the pH to 4 with hydrochloric acid, and a white solid precipitates. After filtration, washing with water and recrystallization with ethanol, 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine is obtained.

[0037] Step 2: Add 1 mol of triazine nucleotide monomer, 1.2 mol of polytetrahydrofuran diol and 1.0 mol of 1,4-butanediol to 2 L of N,N-dimethylformamide, add p-toluenesulfonic acid as a catalyst, and react at 140 °C for 8 h. After the reaction is completed, remove the solvent by vacuum distillation to obtain hyperbranched triazine-polyether ester intermediate.

[0038] Step 3: Add 1 mol of the above hyperbranched triazine-polyether ester intermediate (based on carboxyl groups), 10 mol of epichlorohydrin and 1 mol of sodium hydroxide to the reaction vessel and react at 70°C for 6 h. After the reaction is completed, filter to remove salts and remove excess epichlorohydrin by vacuum distillation to obtain terminal glycidyl hyperbranched triazine-polyether ester oligomer.

[0039] Step 4: Weigh 5 parts of terminal glycidyl hyperbranched triazine-polyether ester oligomer, 94 parts of polyether thermoplastic polyurethane, and 1 part of aminosilane-modified nano silica particles (30 nm primary particle size). Premix them in a mixer for 5 min. Add the premix to a twin-screw extruder for melt blending (screw speed 350 rpm, zone temperatures 190℃, 210℃, 240℃, 260℃, 245℃) and extrude to granulate, to obtain a high-impact polymer modifier with synergistic toughening of nanostructure.

[0040] Comparative Example 1: The difference between this comparative example and Example 1 is that it lacks the terminal glycidyl hyperbranched triazine-polyether ester oligomer, while the other steps are the same as in Example 1.

[0041] Comparative Example 2: The difference between this comparative example and Example 1 is that it lacks a nano-morphology modifier; the rest of the steps are the same as in Example 1.

[0042] Comparative Example 3: The difference between this comparative example and Example 1 is that unmodified nano-silica particles are used instead of aminosilane-modified nano-silica particles.

[0043] Performance testing

[0044] The polymer modifiers prepared in Examples 1-4 and Comparative Examples 1-3 were premixed with polybutylene terephthalate (PBT) matrix resin at a mass ratio of 20:80. Then, they were added to a twin-screw extruder (temperature zones of 190°C, 210°C, 240°C, 260°C, and 245°C) for melt blending and extrusion granulation. Standard test strips were then prepared by injection molding (injection temperature of 255°C and mold temperature of 80°C).

[0045] 1. Mechanical property testing

[0046] The notched impact strength of the specimen was determined according to GB / T 1843-2008 standard. The tensile properties of the specimen were determined according to GB / T 1040.2-2022 standard. The flexural properties of the specimen were determined according to GB / T 9341-2008 standard.

[0047] Table 1. Test results of mechanical properties of the spline

[0048] sample <![CDATA[Izod impact strength (kJ / m 2 )]]> Tensile strength (MPa) Elongation at break (%) Bending strength (MPa) Example 1 18.6±1.2 48.3±1.5 95.6±8.0 73.2±1.8 Example 2 24.8±1.6 52.1±1.3 128.4±7.5 78.5±1.7 Example 3 21.3±1.4 49.6±1.6 112.7±9.4 75.4±1.9 Example 4 20.1±1.3 52.5±1.4 109±5.3 72.3±1.2 Comparative Example 1 7.2±0.8 38.5±1.2 68.5±6.8 58.6±1.0 Comparative Example 2 10.5±1.0 44.7±1.1 75.2±6.9 67.3±1.5 Comparative Example 3 13.2±1.1 42.6±1.3 25.0±3.7 65.8±1.6

[0049] As shown in Table 1, the notched impact strength of Examples 1-4 is 18.6-24.8 kJ / m. 2 Comparison Example 1 (7.2 kJ / m 2 The increase was 158%-244%, compared to control sample 2 (10.5 kJ / m³). 2 The efficiency increased by 77%-136%, compared to control sample 3 (13.2 kJ / m³). 2The improvement ranged from 41% to 88%. This significant difference stemmed from the synergistic regulation of interfacial bonding strength and dispersed phase morphology. In Examples 1-4, the glycidyl-terminated hyperbranched triazine-polyether ester oligomers contained multiple glycidyl groups. During melt blending, these groups underwent a ring-opening reaction with the terminal carboxyl groups of the PBT matrix, forming interfacial chemical bonds and significantly improving the interfacial bonding strength between the modifier and the matrix. Simultaneously, the fibrillable polymer phase formed a fibrous dispersed phase in situ under shear field action, efficiently absorbing impact energy through fiber bridging and stress transfer mechanisms. The nanomorphology modifier interacted with the hyperbranched oligomers through chemical bonds formed by its surface amino groups, effectively inhibiting the shrinkage and co-aggregation of the fibrous dispersed phase, ensuring the stability of the fiber morphology and a high aspect ratio. In Comparative Example 1, due to the lack of hyperbranched oligomers, the interface relied solely on physical entanglement, resulting in low bonding strength, a spherical dispersed phase that was prone to debonding, and an impact strength of only 7.2 kJ / m. 2 Comparative Example 2, lacking nano-morphology modifiers, exhibited unstable fiber morphology, was prone to shrinkage, and had an impact strength of only 10.5 kJ / m. 2 Comparative Example 3, due to the use of unmodified nanoparticles, resulted in particle aggregation and weak interfacial interactions, leading to partial damage to the fiber morphology and an impact strength of only 13.2 kJ / m. 2 .

[0050] In terms of tensile and flexural properties, the tensile strength (48.3-52.5 MPa) and flexural strength (72.3-78.5 MPa) of Examples 1-4 were significantly better than those of Comparative Examples 1-3. Comparative Example 1, due to weak interfacial bonding, could not effectively transfer stress, resulting in the most significant decrease in tensile strength (38.5 MPa) and flexural strength (58.6 MPa). Comparative Example 2 lacked the morphological stabilizing effect of nanoparticles, leading to easy fiber aggregation and shrinkage, resulting in tensile strength (44.7 MPa) and flexural strength (67.3 MPa) still lower than the Examples. Comparative Example 3 used unmodified nanoparticles, which agglomerated into stress concentration points, preferentially initiating cracks during tensile and flexural processes, leading to a decrease in tensile strength (42.6 MPa) and flexural strength (65.8 MPa).

[0051] 2. Dynamic mechanical performance testing

[0052] The dynamic mechanical properties of the specimens were determined in accordance with GB / T 9870.1-2006 standard.

[0053] Table 2 Dynamic mechanical properties of splines

[0054] sample Glass transition temperature (°C) Energy storage modulus E' @25℃ (MPa) Energy storage modulus E' @80℃ (MPa) Peak loss factor tan δ peak temperature (°C) Example 1 65.4 1850±45 820±25 0.085±0.005 68.2 Example 2 64.2 1980±40 890±22 0.078±0.004 69.5 Example 3 63.1 1910±42 850±24 0.082±0.005 68.7 Example 4 63.9 1940±41 830±20 0.079±0.003 68.1 Comparative Example 1 58.3 1620±38 680±26 0.112±0.008 64.6 Comparative Example 2 60.8 1750±40 750±23 0.098±0.006 66.3 Comparative Example 3 61.5 1680±39 710±21 0.105±0.007 65.8

[0055] As shown in Table 2, the glass transition temperatures (63.1-65.4℃) of Examples 1-4 were significantly higher than those of Comparative Examples 1-3 (58.3-61.5℃). This is mainly because the glycidyl-terminated hyperbranched triazine-polyether ester oligomers formed interfacial chemical bonds with the PBT matrix, restricting the mobility of the molecular chains. The room-temperature storage modulus (1850-1980 MPa) and high-temperature storage modulus (820-890 MPa) of Examples 1-4 were both higher than those of Comparative Examples 1-3. This is attributed to the network reinforcement structure formed by the fibrous dispersed phase and the stabilizing effect of the nano-morphology modifier on the fiber morphology. The peak values ​​of the loss factors in Examples 1-4 (0.078-0.085) were lower than those in Comparative Examples 1-3 (0.098-0.112), and Example 2 had the lowest loss factor when the toughening effect was optimal. This indicates that the energy dissipation mainly stems from the effective toughening mechanism of fiber deformation and interfacial friction, rather than the ineffective energy dissipation caused by interfacial slippage or incomplete fiber structure in the comparative examples.

[0056] In comparison, Comparative Example 1 lacks hyperbranched oligomers, and the interface relies solely on physical entanglement. It has the lowest glass transition temperature (58.3℃), and its storage modulus (1620 / 680MPa) is significantly lower than the Example, while its peak loss factor (0.112) is the highest. Comparative Example 2 lacks nano-morphology modifiers, resulting in unstable fiber morphology and easy shrinkage. Its glass transition temperature (60.8℃) and storage modulus (1750 / 750MPa) are lower than the Example, but its peak loss factor (0.098) is still relatively high. Comparative Example 3 uses unmodified nanoparticles, and particle aggregation disrupts interfacial bonding and fiber stability. Its glass transition temperature (61.5℃) and storage modulus (1680 / 710MPa) are both lower than the Example, but its peak loss factor (0.105) is relatively high, and its structure retention at high temperatures is the worst.

[0057] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A high-impact polymer modifier with synergistic toughening through nanostructures, characterized in that, The polymer modifier comprises the following components in parts by weight: 5-15 parts of terminal glycidyl hyperbranched triazine-polyether ester oligomer, 82-94 parts of fiberizable polymer phase, and 1-3 parts of nanomorphology modifier. The preparation method of the terminal glycidyl hyperbranched triazine-polyether ester oligomer is as follows: Cyanurium chloride, p-hydroxybenzoic acid, and a base are added to an acetone / water mixed solvent in a molar ratio of 1:(3.0-3.6):(3.0-6.0). The reaction is carried out under stepwise temperature control. After the reaction is completed, the pH is adjusted to 2-4, a solid is precipitated and purified to obtain 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine. Triazine nucleotide monomer, polytetrahydrofuran glycol, and 1,4-butanediol are added to N,N-dimethylformamide in a molar ratio of 1:(0.3-1.2)(0.2-1.5). An esterification polycondensation reaction is carried out in the presence of a catalyst to obtain a hyperbranched triazine-polyether ester intermediate. The intermediate is reacted with epichlorohydrin to carry out a glycidylation reaction to obtain the terminal glycidyl hyperbranched triazine-polyether ester oligomer.

2. The high-impact polymer modifier with synergistic toughening of nanostructures according to claim 1, characterized in that, The fibrillable polymer phase is a thermoplastic polyester elastomer or a thermoplastic polyurethane.

3. The high-impact polymer modifier with synergistic toughening of nanostructures according to claim 1, characterized in that, The nanomorphology modifier is an aminosilane-modified nano-silica particle with a primary particle size of 10-50 nm.

4. The high-impact polymer modifier with synergistic toughening of nanostructures according to claim 1, characterized in that, The stepwise temperature control is specifically as follows: the first substitution reaction is carried out at 0-10℃ for 1-4 hours, and then the temperature is increased to 35-60℃ for 2-8 hours to complete the subsequent substitution reaction; the temperature of the esterification polycondensation reaction is 140-180℃, the reaction time is 4-12 hours, and the catalyst is selected from at least one of p-toluenesulfonic acid, titanate catalyst or tin-based catalyst; the temperature of the glycidylation reaction is 40-90℃, the reaction time is 2-10 hours.

5. The high-impact polymer modifier with synergistic toughening of nanostructures according to claim 1, characterized in that, In the glycidylation reaction, the molar ratio of carboxyl group, epichlorohydrin and base in the hyperbranched triazine-polyether ester intermediate is 1:(2-10):(1-3).

6. The high-impact polymer modifier with synergistic toughening of nanostructures according to any one of claims 1-5, characterized in that, The preparation method of the modifier is as follows: first, the terminal glycidyl hyperbranched triazine-polyether ester oligomer, the fiberizable polymer phase and the nano-morphology modifier are premixed, and then added to a twin-screw extruder for melt blending and granulation to obtain the polymer modifier; wherein, the screw speed of the twin-screw extruder is 150-500 rpm and the temperature is 190-260℃.

7. The application of the nanostructure synergistic toughening high-impact polymer modifier according to any one of claims 1-5 in the preparation of high-impact polymer materials.

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