Nano titanium dioxide composite resin material and preparation method thereof

Abstract

The invention discloses a nano titanium dioxide composite resin material and a preparation method thereof, and belongs to the technical field of composite materials. The material is composed of an epoxy resin material, nano titanium dioxide, a dispersing agent, a coupling agent, rubber powder, calcium carbonate, a specific structure stabilizer and a curing agent, the stabilizer comprises aromatic rings and alkyl / deuterated alkyl substituent groups, interface bonding force is enhanced through pi-pi accumulation, hydrogen bonds and a dynamic stabilization effect, agglomeration of nano particles is inhibited, and the stability of the material is improved. The thermal stability and the ultraviolet aging resistance of the material are synergistically improved. The preparation method comprises the following steps: pretreating the raw materials, modifying the surface of the nano titanium dioxide through a coupling agent, uniformly dispersing all the components by adopting shear emulsification and vacuum stirring, and performing staged curing molding. By optimizing the component synergistic effect and process parameters, the mechanical strength, impact resistance and weather resistance of the material are remarkably improved, the curing efficiency is high, the process stability is high, and the method is suitable for large-scale production.

Description

Technical Field

[0001] The present invention relates to the technical field of composite materials, and in particular to a nano titanium dioxide composite resin material and a preparation method thereof. Background Art

[0002] In modern industrial applications, epoxy resin composites are widely used due to their excellent mechanical properties and chemical resistance. However, their stability has always been a key bottleneck restricting their further development. Epoxy resin materials are easily affected by environmental factors during long-term use, resulting in unstable performance, which is mainly reflected in the following aspects:

[0003] First, epoxy resin materials are extremely sensitive to temperature and humidity fluctuations. In high-temperature or high-humidity environments, the molecular chains within the material migrate or absorb water and expand, resulting in a decrease in mechanical properties, such as strength and modulus. Furthermore, temperature fluctuations can cause inconsistencies in the material's coefficient of thermal expansion, leading to the generation of internal stresses, further exacerbating material instability and the risk of cracking.

[0004] Secondly, epoxy resin materials undergo photodegradation under prolonged exposure to UV light. UV light breaks down the chemical bonds within the epoxy resin's molecular chains, causing surface cracking, discoloration, and performance degradation. This photoaging phenomenon not only affects the material's appearance but also significantly reduces its weather resistance and service life.

[0005] Furthermore, the curing process of epoxy resin materials can also introduce internal stress. During the curing process, as the epoxy resin transitions from liquid to solid, volume shrinkage is inevitable, leading to the accumulation of internal stress. When internal stress exceeds the material's tolerance limit, the material is prone to cracking or delamination, affecting its long-term stability.

[0006] To address these issues, researchers have attempted to improve the stability of epoxy resin materials by adding nanomaterials (such as nano-titanium dioxide). However, nanomaterials have poor dispersibility in the epoxy resin matrix and are prone to agglomeration, resulting in the material's performance not being fully utilized. In addition, the interfacial bonding between the nanomaterials and the epoxy resin matrix is weak, further limiting their enhancement effect. These issues have limited the effectiveness of existing technologies in improving material stability.

[0007] While existing methods such as surface modification and coupling agent treatment can partially improve the dispersibility of nanomaterials, these processes are complex and their effects are unstable, making them difficult to apply in large-scale production. Therefore, developing a new material and its preparation process that can effectively address the stability issues of epoxy resin composites is of great theoretical and practical significance.

[0008] In response to the above problems, the present invention proposes a nano-titanium dioxide composite resin material and its preparation process. By optimizing the material formula and process parameters, the stability of the material is significantly improved, providing reliable technical support for the application of epoxy resin composite materials in high-end fields. Summary of the Invention

[0009] The purpose of the present invention is to provide a nano-titanium dioxide composite resin material and a preparation method thereof to address the shortcomings of existing epoxy resin composite materials in terms of stability. By optimizing the material formula and process parameters, the stability of the material is significantly improved, while also improving its mechanical properties, impact resistance and weather resistance.

[0010] To achieve the above object, the technical solution adopted by the present invention is: a nano-titanium dioxide composite resin material, composed of the following components in percentage by mass: 50-90 parts of resin material, 1-15 parts of nano-titanium dioxide, 0.5-3 parts of dispersant, 0.5-5 parts of coupling agent, 2-8 parts of rubber powder, 5-20 parts of calcium carbonate, 0.1-2 parts of stabilizer, and 0.1-1 parts of curing agent;

[0011] The resin material is an epoxy resin material;

[0012] The structure of the stabilizer is the structure shown in Formula I;

[0013]

[0014] Wherein R1 is selected from: C1-C6 alkyl, C1-C6 deuterated alkyl, C6-C 10 Aryl, C4-C 10 heteroaryl;

[0015] or R1 is selected from: C6-C6 alkyl, C1-C6 deuterated alkyl substituted 10 Aryl, C4-C 10 of heteroaryl.

[0016] Furthermore, the epoxy resin material is selected from one or more of bisphenol A epoxy resin, epoxy resin-1001, and bisphenol F epoxy resin.

[0017] Furthermore, the particle size of the nano titanium dioxide is 10-50 nm.

[0018] Furthermore, the dispersant is selected from one or more of polyvinyl pyrrolidone, polyvinyl alcohol, sodium polyacrylate, and polymaleic anhydride.

[0019] Furthermore, the coupling agent is γ-aminopropyltriethoxysilane and / or γ-methacryloxypropyltrimethoxysilane.

[0020] Furthermore, the curing agent is selected from one or more of ethylenediamine, diethylenetriamine, and methyltetrahydrophthalic anhydride.

[0021] Furthermore, the rubber powder is obtained by crushing waste tires into powder.

[0022] Furthermore, the C1-C6 alkyl group is selected from the group consisting of: methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0023] Furthermore, the C1-C6 deuterated alkyl group is selected from the group consisting of: deuterated methyl, deuterated ethyl, and deuterated butyl.

[0024] Furthermore, the C6-C 10 The aryl group is selected from: phenyl.

[0025] Furthermore, the C4-C 10 Heteroaryl: furyl, thienyl.

[0026] Furthermore, the structure of the stabilizer is:

[0027]

[0028] Furthermore, the synthesis steps of the stabilizer are:

[0029]

[0030] Step 1: Add raw material 1 (2.1 eq), raw material 2 (1.0 eq), sodium tert-butoxide (3 eq), Pd2(dba)3 (0.02 eq), and tri-tert-butylphosphine (1 eq) to toluene (10 times the mass of raw material 1), and heat reflux under nitrogen for 12 hours. Extract with dichloromethane and distilled water, retain the organic phase, wash the organic phase with brine 1-2 times, retain the organic phase, spin-dry at 40-55°C, add ethanol (2 times the mass of the spin-dried solid), heat reflux at 90°C for 1 hour, pass through silica gel cake while hot, and spin-dry to obtain intermediate 1;

[0031] Step 2: Add intermediate 1 (1 eq) to tetrahydrofuran (10 times the mass of intermediate 1), stir to dissolve, add 1,3-dibromo-5,5-dimethylhydantoin (3.1 eq), stir at 60°C for 6-8 hours, and after the reaction is complete, add water to the reaction system for extraction, retain the organic phase, dry the organic phase with anhydrous magnesium sulfate, spin-dry at 40-55°C, pass through a silica gel column, and spin-dry to obtain intermediate 2;

[0032] Step 3: Add intermediate 2 (1 eq) and raw material 3 (2.2 eq) to a glass reaction bottle, then add dimethyl sulfoxide (10 times the mass of intermediate 2) and stir until completely dissolved, then weigh sodium phosphate (4 eq) and cuprous iodide (1 eq) and add them to the above glass reaction bottle, replace nitrogen in the glass reaction bottle three times, so that the single-mouth glass reaction bottle is placed in an inert gas environment, first heat to 90 ° C, stir and react for 1 hour, then heat to 120 ° C and heat to react for 6 hours, spin dry at 40-55 ° C, and pass through a silica gel column to obtain a stabilizer.

[0033] Furthermore, the silica gel in the silica gel column is 200-300 mesh, the amount of silica gel used is 20 times the amount of the sample, and the silica gel filling volume is 3 / 4 of the column volume.

[0034] Furthermore, the silica gel column is loaded with a dry method.

[0035] The stabilizer involved in the present invention has a core structure as shown in Formula I. Specifically, the stabilizer contains an aromatic ring structure, and the functional group can form an intermolecular interaction with the ring structure of the epoxy resin material through π-π stacking, thereby significantly enhancing the interfacial bonding force. In addition, the stabilizer also contains an alkyl group or a deuterated alkyl group, which makes the material hydrophobic. At the same time, the heteroatoms in the stabilizer, such as nitrogen (N) or oxygen (O), can form hydrogen bonds with the hydroxyl groups on the surface of nano-titanium dioxide, effectively inhibiting the agglomeration of nanoparticles. In terms of dynamic stabilization function, the aromatic ring structure of the stabilizer has high thermal resistance and can delay the degradation process of the resin chain segment at high temperature. In addition, the conjugated system of the stabilizer can absorb ultraviolet rays with a wavelength in the range of 280-400nm, and produce a synergistic effect with the photocatalytic effect of nano-titanium dioxide.

[0036] The stabilizer of the present invention can produce significant synergistic effects with epoxy resin materials, nano-titanium dioxide, and rubber powder or fillers. In terms of synergy with epoxy resin materials, the basic groups of the stabilizer can adjust the curing reaction rate, thereby reducing internal stress. At the same time, the flexible alkyl chain segments in the stabilizer can interpenetrate with the resin cross-linked network, thereby improving the impact strength of the material. In the synergistic effect with nano-titanium dioxide, the silanol groups on the surface of the nano-titanium dioxide modified with a silane coupling agent can form ester bonds with the carboxyl groups of the stabilizer, achieving nanoscale dispersion. In addition, the stabilizer can capture photogenerated holes generated by the nano-titanium dioxide, inhibiting the photooxidation reaction of the resin. In terms of synergistic effect with rubber powder or fillers, the polar groups of the stabilizer can react with the carboxylated surface of the rubber powder, improving compatibility. At the same time, the calcium carbonate particles can form a "core-shell" structure under the wrapping of the stabilizer, thereby improving the modulus of the material.

[0037] The stabilizer of the present invention exhibits significant synergistic effects at the system level. First, nano-titanium dioxide (for UV shielding), stabilizer (for free radical capture), and rubber powder (for crack passivation) together form a three-level protection system. Second, the stabilizer exhibits a recycling and synergistic mechanism. The sulfides in the rubber powder from scrap tires can form metal thiolate complexes with the stabilizer, effectively inhibiting the catalytic degradation of heavy metal ions.

[0038] A method for preparing a nano-titanium dioxide composite resin material comprises the following steps:

[0039] S1 pretreatment: drying the nano-titanium dioxide at 80-100 ° C for 2-4 hours, grinding and sieving the rubber powder to a particle size of ≤ 200 mesh, and preheating the epoxy resin material to 40-50 ° C;

[0040] S2. Surface modification of nano-titanium dioxide: The coupling agent and anhydrous ethanol were mixed in a mass ratio of 1:5-10, stirred and dissolved, and the nano-titanium dioxide pretreated in S1 was added. Ultrasonic dispersion was performed for 30-60 minutes, followed by reaction at 60-80°C for 2-4 hours, centrifuged and dried to obtain modified nano-titanium dioxide;

[0041] S3 mixing and dispersion: The epoxy resin material pretreated in S1 and the dispersant were stirred at 50-60 ° C, 500-800 rpm for 20-30 minutes to form a homogeneous resin matrix, the modified nano-titanium dioxide was added to the resin matrix in batches, dispersed in a shear emulsifier for 40-60 minutes, and the rubber powder, the calcium carbonate and the stabilizer were added sequentially and stirred under vacuum conditions for 1-2 hours;

[0042] S4. Curing and molding: adding the curing agent, maintaining at 40-60°C for 2-4 hours, raising the temperature to 100-120°C, maintaining the temperature for 3-6 hours, cooling and demolding to obtain a nano-titanium dioxide composite resin material.

[0043] Furthermore, the rotation speed of the shear emulsifier is 3000-5000 rpm.

[0044] Furthermore, the vacuum condition is between -0.08 and -0.1 MPa.

[0045] The preparation method of the nano-titanium dioxide composite resin material of the present invention has the following characteristics: the nano-titanium dioxide, rubber powder and epoxy resin materials are optimized through the pretreatment step to ensure the uniformity and stability of the subsequent reaction; the surface modification process of the nano-titanium dioxide adopts a mixed system of a coupling agent and anhydrous ethanol, combined with ultrasonic dispersion and high-temperature reaction, which significantly improves the dispersibility of the nanoparticles and the interfacial bonding force with the resin matrix; the mixing and dispersion step adopts a combination of a shear emulsifier and a vacuum stirring method to ensure the uniform distribution of the modified nano-titanium dioxide, rubber powder, calcium carbonate and stabilizer in the resin matrix, while effectively reducing the residual bubbles; the curing molding step optimizes the uniformity of the curing reaction and the mechanical properties of the material through staged temperature control. The method is simple to operate, has high process stability, is suitable for large-scale production, and the composite material obtained has excellent mechanical properties, thermal stability and aging resistance, and is suitable for a variety of high-performance application scenarios.

[0046] Application of nano-titanium dioxide composite resin material in equipment casing material.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] 1. Significantly improve material properties: This invention significantly improves the tensile strength, flexural strength, impact strength and heat distortion temperature of nano-titanium dioxide composite resin materials. For example, the tensile strength reaches 90.7MPa, the flexural strength reaches 143.6MPa, and the impact strength reaches 20.9kJ / m 2 , heat deformation temperature reaches 156℃, UV aging retention rate is as high as 98.1%, and curing time is only 8.8 hours. These performance improvements have broadened the application of the material in high-end equipment housings and other fields.

[0049] 2. Significantly Enhanced Stability: By introducing a stabilizer with a specific structure, this invention addresses the problem of unstable performance during long-term use of epoxy resin composites. Through π-π stacking, hydrogen bonding, and dynamic stabilization, the stabilizer enhances interfacial bonding and aging resistance, slows high-temperature degradation of the resin, inhibits photodegradation, and improves the material's stability and durability in harsh environments.

[0050] 3. Optimized preparation process and improved efficiency: This invention optimizes the pretreatment, surface modification, mixing and dispersion, and curing steps to ensure uniform dispersion and efficient bonding of nano-titanium dioxide. The surface modification process combines ultrasonic dispersion with high-temperature reaction to enhance nanoparticle dispersibility; mixing and dispersion utilizes shear emulsification and vacuum stirring to ensure uniform distribution of components; and curing utilizes staged temperature control to optimize curing reaction uniformity and mechanical properties. The process is simple and stable, making it suitable for large-scale production.

[0051] 4. Expanding Applications and Improving Cost-Effectiveness: The material of this invention exhibits excellent mechanical properties, aging resistance, hydrophobicity, and impact resistance, making it suitable for high-performance applications in aerospace, automotive, electronics, and other fields. It is stable and durable in harsh environments, reducing maintenance costs. Furthermore, using waste tire rubber powder as a raw material is not only environmentally friendly but also reduces production costs and improves cost-effectiveness. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 This is the step for synthesizing the stabilizer of the present invention. DETAILED DESCRIPTION

[0053] The technical solutions of the present invention will be described clearly and completely below in conjunction with the accompanying drawings of the present invention. Obviously, the embodiments described are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. The materials involved in the embodiments of the present invention and the comparative examples are all purchased from the market.

[0054] Example 1-1

[0055] Synthesis of stabilizer 1:

[0056]

[0057] Step 1: Add raw material 1 (2.1 eq), raw material 2 (1.0 eq), sodium tert-butoxide (3 eq), Pd2(dba)3 (0.02 eq), and tri-tert-butylphosphine (1 eq) to toluene and stir under reflux for 12 hours under nitrogen. Extract with dichloromethane and distilled water, retain the organic phase, wash the organic phase with brine 1-2 times, retain the organic phase, spin dry, add ethanol to the spin-dried solid, reflux for 1 hour, pass through silica gel cake while hot, and spin dry to obtain intermediate 1;

[0058] Step 2: Add intermediate 1 (1 eq) to tetrahydrofuran, stir to dissolve, add 1,3-dibromo-5,5-dimethylhydantoin (3.1 eq), stir at 60°C for 6-8 h, and after the reaction is complete, add water to the reaction system for extraction, retain the organic phase, dry the organic phase with anhydrous magnesium sulfate, spin dry, pass through a silica gel column, and spin dry to obtain intermediate 2;

[0059] Step 3: Intermediate 2 (1 eq) and raw material 3 (2.2 eq) were added to a glass reaction flask, followed by dimethyl sulfoxide (DMSO) and stirring until completely dissolved. Sodium phosphate (4 eq) and cuprous iodide (1 eq) were then weighed and added to the glass reaction flask. The nitrogen atmosphere in the glass reaction flask was evacuated three times to place the single-necked glass reaction flask in an inert gas atmosphere. The temperature was first raised to 90°C and stirred for 1 hour, then raised to 120°C and heated for 6 hours. The mixture was then spin-dried and passed through a silica gel column to obtain stabilizer 1. Compound characterization data: MS (MS+1): 787.

[0060] Referring to the synthesis steps of Example 1-1, Examples 1-2 to 1-7 were prepared, wherein the raw material 3 was different from that of Example 1-1, and the rest were the same as Example 1-1. The specific structure of raw material 3, compound characterization data, and stabilizer structure are shown in Table 1.

[0061] Table 1. Structure of raw material 3, structure of stabilizer, and characterization data of compounds.

[0062]

[0063]

[0064] Example 1

[0065] A preparation method of a nano-titanium dioxide composite resin material comprises the following steps:

[0066] S1 pretreatment: 8 parts of nano-titanium dioxide were dried at 100 ° C for 4 hours, 4 parts of rubber powder were ground and sieved to a particle size of ≤ 200 mesh, and 72 parts of bisphenol A epoxy resin were preheated to 40-50 ° C;

[0067] S2. Surface modification of nano-titanium dioxide: 2 parts of γ-aminopropyltriethoxysilane and anhydrous ethanol were mixed in a mass ratio of 1:8, stirred and dissolved, and the nano-titanium dioxide treated in S1 was added. Ultrasonic dispersion was performed for 60 minutes, followed by reaction at 80°C for 4 hours. The mixture was centrifuged and dried to obtain modified nano-titanium dioxide.

[0068] S3 mixing and dispersion: The treated bisphenol A epoxy resin and polyvinyl alcohol in S1 were stirred at 60 ° C and 800 rpm for 30 minutes to form a homogeneous resin matrix, the modified nano-titanium dioxide was added to the resin matrix in batches, dispersed at 3000 rpm in a shear emulsifier for 60 minutes, followed by 5 parts of rubber powder, 6 parts of calcium carbonate and 2 parts of a stabilizer (stabilizer 1 synthesized in Example 1-1), and stirred under vacuum for 2 hours;

[0069] S4. Curing and molding: Add 1 part of ethylenediamine, maintain at 60°C for 4 hours, raise the temperature to 120°C, maintain for 6 hours, cool and demold to obtain a nano-titanium dioxide composite resin material.

[0070] Example 2

[0071] Referring to the method for preparing a nano-titanium dioxide composite resin material in Example 1, the stabilizer in Example 1 was replaced with (stabilizer 3 synthesized in Example 1-2), and the rest remained unchanged.

[0072] Example 3

[0073] Referring to the method for preparing a nano-titanium dioxide composite resin material in Example 1, the stabilizer in Example 1 was replaced with (stabilizer 6 synthesized in Example 1-3), and the rest remained unchanged.

[0074] Example 4

[0075] Referring to the method for preparing a nano-titanium dioxide composite resin material in Example 1, the stabilizer in Example 1 was replaced with (stabilizer 8 synthesized in Examples 1-4), and the rest remained unchanged.

[0076] Example 5

[0077] Referring to the method for preparing a nano-titanium dioxide composite resin material in Example 1, the stabilizer in Example 1 was replaced with (stabilizer 11 synthesized in Example 1-5), and the rest remained unchanged.

[0078] Example 6

[0079] Referring to the method for preparing a nano-titanium dioxide composite resin material in Example 1, the stabilizer in Example 1 was replaced with (stabilizer 14 synthesized in Example 1-6), and the rest remained unchanged.

[0080] Example 7

[0081] Referring to the method for preparing a nano-titanium dioxide composite resin material in Example 1, the stabilizer in Example 1 was replaced with (stabilizer 17 synthesized in Example 1-7), and the rest remained unchanged.

[0082] Example 8

[0083] Referring to the method for preparing a nano-titanium dioxide composite resin material in Example 1, the bisphenol A epoxy resin in Example 1 was replaced with epoxy resin-1001, and the rest remained unchanged.

[0084] Example 9

[0085] Referring to the method for preparing a nano-titanium dioxide composite resin material in Example 1, the polyvinyl alcohol in Example 1 was replaced with polyvinyl pyrrolidone, and the rest remained unchanged.

[0086] Comparative Example 1

[0087] The preparation method was similar to that in Example 1, but without adding a stabilizer and other conditions remained unchanged.

[0088] Comparative Example 2

[0089] The preparation method of Example 1 was referred to, except that the bisphenol A epoxy resin in Example 1 was not replaced with acrylic resin, and the rest remained unchanged.

[0090] The structure of the acrylic resin is Molecular weight: 70,000.

[0091] Comparative Example 3

[0092] The preparation method was similar to that in Example 1, except that γ-aminopropyltriethoxysilane was not added and the rest remained unchanged.

[0093] Comparative Example 4

[0094] The preparation method was similar to that in Example 1, except that ethylenediamine was not added and the rest remained unchanged.

[0095] Performance testing:

[0096] 1. Tensile Strength: Tensile strength was determined in accordance with ASTM D638. The prepared composite material was processed into a standard dumbbell-shaped specimen and tested using a material testing machine at a tensile rate of 5 mm / min. The maximum tensile stress at fracture was recorded in megapascals (MPa).

[0097] 2. Determination of flexural strength: Process the composite material into a standard rectangular specimen and perform a three-point bending test using a material testing machine at a bending rate of 2 mm / min. Record the maximum bending stress at fracture of the specimen in megapascals (MPa).

[0098] 3. Determination of impact strength: Process the composite material into a standard cantilever beam specimen and test it using a pendulum impact tester. Record the impact energy when the specimen breaks in kilojoules per square meter (kJ / m 2 ).

[0099] 4. Determination of heat distortion temperature: Process the composite material into a standard specimen and test it using a heat distortion temperature tester under a load of 1.8 MPa at a heating rate of 120°C / h. Record the temperature when the specimen deforms 0.25 mm in degrees Celsius (°C).

[0100] 5. Determination of UV aging retention rate: Place the composite material sample in a QUV accelerated aging test chamber, set the UV wavelength to 340nm, the relative humidity to 50 parts, the cycle to 8 hours of illumination and 4 hours of condensation, and after 500 hours of aging, test the tensile strength or flexural strength of the sample and compare it with the performance data before aging to calculate the retention rate in percentage (parts).

[0101] 6. Determination of Curing Time: Place the composite resin system (approximately 10 mg) in the DSC sample pan and heat to 180°C at a heating rate of 10°C / min. Record the start and end times of the curing reaction. The curing time is defined as the time required for 90 copies of the curing reaction to complete, expressed in hours (h). Observation can also be used to assist in verification, recording the time required for the material to completely transform from a liquid to a solid state.

[0102] The performance data of tensile strength, flexural strength, impact strength, heat deformation temperature, UV aging retention rate and curing time are shown in Table 2.

[0103] Table 2. Performance data of tensile strength, flexural strength, impact strength, heat distortion temperature, UV aging retention rate, and curing time

[0104]

[0105] The performance test data show that by adjusting the stabilizer structure in Examples 1-7, the tensile strength, flexural strength, impact strength and heat deformation temperature of the material show a trend of first increasing and then decreasing, among which Example 7 achieves the best performance (tensile strength 90.7MPa, flexural strength 143.6MPa, impact strength 20.9kJ / m 2 , heat distortion temperature 156 ℃), while the UV aging retention rate is as high as 98.1 parts, and the curing time is shortened to 8.8 hours. After the epoxy resin material or dispersant in Examples 8 and 9 was replaced, the performance indicators dropped significantly (for example, the impact strength of Example 8 dropped to 15.3 kJ / m 2 ), the curing time was extended to more than 12 hours. Comparative Examples 1-4 significantly deteriorated in performance due to the lack or replacement of key components. The data show that the molecular design of the stabilizer has a decisive influence on the overall performance of the material. The formulation of Example 7 performed optimally in terms of mechanical properties, thermal stability, and aging resistance, with significantly improved curing efficiency, validating the technical advantages of the present invention in optimizing material stability.

[0106] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A nano-titanium dioxide composite resin material, characterized in that: The invention is composed of the following components in percentage by mass: 50-90 parts of resin material, 1-15 parts of nano titanium dioxide, 0.5-3 parts of dispersant, 0.5-5 parts of coupling agent, 2-8 parts of rubber powder, 5-20 parts of calcium carbonate, 0.1-2 parts of stabilizer, and 0.1-1 parts of curing agent; The resin material is an epoxy resin material; The curing agent is one or more of ethylenediamine, diethylenetriamine, and methyltetrahydrophthalic anhydride; The structure of the stabilizer is a compound shown in Formula I; Wherein R1 is selected from: C1-C6 alkyl, C1-C6 deuterated alkyl, C6-C 10 Aryl, C4-C 10 heteroaryl; or R1 is selected from: C6-C6 alkyl, C1-C6 deuterated alkyl substituted 10 Aryl, C4-C 10 of heteroaryl.

2. A nano-titanium dioxide composite resin material according to claim 1, characterized in that: The epoxy resin material is selected from one or more of bisphenol A epoxy resin, epoxy resin-1001, and bisphenol F epoxy resin.

3. The nano-titanium dioxide composite resin material according to claim 1, characterized in that: The dispersant is selected from one or more of polyvinyl pyrrolidone, polyvinyl alcohol, sodium polyacrylate, and polymaleic anhydride.

4. The nano-titanium dioxide composite resin material according to claim 1, characterized in that: The coupling agent includes γ-aminopropyltriethoxysilane and / or γ-methacryloxypropyltrimethoxysilane.

5. The nano-titanium dioxide composite resin material according to claim 1, characterized in that: The rubber powder is obtained by crushing waste tires into powder.

6. The nano-titanium dioxide composite resin material according to claim 1, characterized in that: The stabilizer is a compound of any one of formula I1 to formula I18:

7. A method for preparing a nano-titanium dioxide composite resin material according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1 pretreatment: drying the nano-titanium dioxide at 80-100 ° C for 2-4 hours to obtain pretreated titanium dioxide; Grinding and sieving the rubber powder to a particle size of ≤200 mesh; preheating the epoxy resin material to 40-50° C. to obtain a pretreated epoxy resin material; S2. Surface modification of nano-titanium dioxide: The coupling agent and anhydrous ethanol were mixed in a mass ratio of 1:5-10, stirred and dissolved, and the nano-titanium dioxide pretreated in S1 was added. Ultrasonic dispersion was performed for 30-60 minutes, followed by reaction at 60-80°C for 2-4 hours, centrifuged and dried to obtain modified nano-titanium dioxide; S3 mixing and dispersion: The epoxy resin material pretreated in S1 and the dispersant were stirred at 50-60 ° C, 500-800 rpm for 20-30 minutes to form a homogeneous resin matrix, the modified nano-titanium dioxide was added to the homogeneous resin matrix in batches, sheared and dispersed for 40-60 minutes, and the rubber powder, calcium carbonate and stabilizer were added sequentially and stirred under vacuum conditions for 1-2 hours; S4. Curing and molding: adding the curing agent, maintaining at 40-60°C for 2-4 hours, raising the temperature to 100-120°C, maintaining the temperature for 3-6 hours, cooling and demolding to obtain a nano-titanium dioxide composite resin material.

8. The method for preparing a nano-titanium dioxide composite resin material according to claim 7, characterized in that: The shearing rotation speed is 3000-5000 rpm.

9. The method for preparing a nano-titanium dioxide composite resin material according to claim 7, characterized in that: The vacuum pressure is -0.08 to -0.1 MPa.

10. Use of the nano-titanium dioxide composite resin material according to any one of claims 1 to 6 in preparing equipment housing materials.

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