Carbon-based silica composite, high-impact low-voc resin composite, and preparation method and application thereof

Abstract

This invention discloses carbon-based silica composite materials, high-impact, low-VOC resin composite materials, their preparation methods, and applications. The carbon-based silica composite material of this invention is a carbon-based silica composite material with silica loaded on the surface of activated carbon fibers. After in-situ synthesis of silica on a carbon source matrix, the composite material is obtained through high-temperature carbonization. This invention utilizes carbon and silicon sources as raw materials to synthesize, in-situ, a mixture containing carbon source and SiO2 in a liquid-phase system. 2 The composite material was then subjected to hydrothermal carbonization to prepare a material containing SiO2. 2 The composite component is composed of activated carbon fiber. The carbon-based silica composite material prepared by this invention has a high specific surface area and excellent adsorption performance. When added to resin as a filler, it can significantly improve the VOC release of the material and at the same time improve the impact resistance of the resin material.

Description

Carbon-based silica composite materials, high-impact, low-VOC resin composite materials, their preparation methods and applications Technical Field

[0001] This invention relates to the technical field of organic-inorganic composite fillers for resins, and more specifically, to carbon-based silica composite materials, high-impact, low-VOC resin composite materials, their preparation methods, and applications. Background Technology

[0002] Currently, the environmental performance of materials is receiving increasing attention. The organic gases released by polymer materials during use are a crucial data point for environmental monitoring. Therefore, developing low-VOC resins with the goal of energy conservation, emission reduction, and environmental pollution reduction is an inevitable trend. The VOCs in polyolefin materials are mainly alkanes and olefins, with some products containing small-molecule oxides, chlorides, benzene compounds, etc. Adding components with good adsorption properties for volatile organic compounds to the resin can reduce the VOC content released into the environment, resulting in low-VOC resin materials.

[0003] Nano-silica is currently the most produced nanoparticle material on a large industrial scale worldwide. Nano-SiO2 has attracted considerable attention due to its inorganic rigidity, high specific surface energy, and strong surface adsorption capacity. Adding a small amount of SiO2 to polypropylene (PP) can alter its structure and interfacial properties, improving the composite material's tensile strength, impact strength, and elongation at break, and playing a role in heterogeneous nucleation, accelerating crystallization, and increasing the crystallization peak temperature during the PP crystallization process. However, because SiO2 is an inorganic component, it is difficult to disperse uniformly in polymers, affecting its applications.

[0004] Activated carbon is a porous carbon-containing material mainly composed of graphite-like microcrystals. Due to its well-developed pore structure, specific surface area, and excellent adsorption properties, it is widely used in many fields such as exhaust gas treatment and air purification.

[0005] Existing technologies typically involve preparing composite materials by simply mixing carbon-based materials with SiO2. However, the resulting composite materials have relatively poor structural stability, which limits further improvements in material performance and restricts their application range. Summary of the Invention

[0006] To address the problems in existing technologies, this invention proposes carbon-based silica composite materials, high-impact, low-VOC resin composite materials, their preparation methods, and applications. This invention utilizes carbon and silicon sources as raw materials to synthesize SiO2 in situ on the carbon source in a liquid-phase system, forming a composite containing both carbon source and SiO2. This composite is then subjected to hydrothermal carbonization to prepare a composite component containing SiO2 and activated carbon fibers. The carbon-based silica composite material prepared by this invention has a very high specific surface area and excellent adsorption properties. When added as a filler to resin, it can significantly improve VOC release and simultaneously enhance the impact resistance of the resin material.

[0007] One objective of this invention is to provide a carbon-based silica composite material, wherein the carbon-based silica composite material is a carbon-based silica composite material with silica loaded on the surface of activated carbon fibers.

[0008] In the carbon-based silica composite material described in this invention, preferably,

[0009] The mass ratio of activated carbon fiber to silicon dioxide in the carbon-based silica composite material is 10:1 to 2:1.

[0010] The second objective of this invention is to provide a method for preparing a carbon-based silica composite material, comprising the following steps:

[0011] After in-situ synthesis of silica on a carbon source matrix, carbon-based silica composite material is obtained by high-temperature carbonization; preferably, the high-temperature carbonization adopts a high-pressure reactor hydrothermal carbonization method.

[0012] The carbon source matrix is ​​selected from modified carbon sources obtained by modifying carbon sources with raw materials including surfactants and alkalis;

[0013] Preferred for the preparation of the carbon-based silica composite material as described in any one of the objectives of this invention.

[0014] In the preparation method of the carbon-based silica composite material of the present invention, preferably, the following steps are included:

[0015] (1) After the organic solvent dispersion, surfactant solution and alkaline solution of the carbon source are mixed evenly, the mixture is soaked, the solid and liquid are separated, the solid is washed and dried under vacuum to obtain the modified carbon source.

[0016] (2) Disperse the modified carbon source evenly in an organic solvent to obtain a suspension;

[0017] (3) Add silicon source solution to suspension, disperse evenly, and carry out hydrothermal reaction in high pressure reactor to obtain carbon-based silicon dioxide composite material.

[0018] In the preparation method of the carbon-based silica composite material of the present invention, preferably,

[0019] In step (1),

[0020] The carbon source is selected from natural plant polymer materials, preferably, the carbon source is selected from at least one of cellulose and hemicellulose;

[0021] More preferably, the molecular weight of the plant-based natural polymer material is 0.5 × 10⁻⁶. 4 ~2.0×10 5 ; and / or,

[0022] The surfactant in the surfactant solution is selected from at least one of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium fatty alcohol sulfate, and sodium succinate sulfonate; and / or,

[0023] The alkali in the alkaline solution is selected from at least one of sodium hydroxide, potassium hydroxide, urea, and ammonia water; and / or,

[0024] The organic solvent in the organic solvent dispersion of the carbon source is selected from at least one of ethanol, acetone, tetrahydrofuran, and ethyl acetate.

[0025] In the preparation method of the carbon-based silica composite material of the present invention, preferably,

[0026] In step (1),

[0027] The mass ratio of the carbon source to the surfactant is 1:1 to 100:1; and / or,

[0028] The mass ratio of the carbon source to the alkali in the alkaline solution is 200:1 to 4:1; and / or,

[0029] The soaking time is 1-5 hours; the soaking in this invention is carried out at room temperature.

[0030] Preferably,

[0031] The concentration of the surfactant solution is 0.5wt-20wt%; and / or,

[0032] The concentration of the alkaline solution is 0.1wt%-5wt%.

[0033] In the preparation method of the carbon-based silica composite material of the present invention, preferably,

[0034] In step (2),

[0035] The organic solvent is selected from at least one of ethanol, acetone, tetrahydrofuran, and ethyl acetate; and / or,

[0036] The mass ratio of modified carbon source to organic solvent is 1:10 to 1:2.

[0037] In the preparation method of the carbon-based silica composite material of the present invention, preferably,

[0038] In step (3),

[0039] The silicon source solution is selected from organic solutions of alkoxysilanes; preferably,

[0040] The alkoxysilane in the silicon source solution is selected from at least one of tetraethyl orthosilicate and tetramethyl orthosilicate; and / or,

[0041] The organic solvent in the silicon source solution is selected from at least one of ethanol, acetone, tetrahydrofuran, and ethyl acetate; and / or,

[0042] The concentration of the silicon source solution is 0.5 wt% to 10 wt%; and / or,

[0043] The mass ratio of alkoxysilanes in the carbon source and silicon source solutions is 40:1 to 4.5:1.

[0044] In the preparation method of the carbon-based silica composite material of the present invention, preferably,

[0045] In step (3),

[0046] Add silicon source solution dropwise to the suspension; and / or,

[0047] The hydrothermal reaction temperature is 160-260℃; and / or,

[0048] The hydrothermal reaction takes 1-3 hours.

[0049] More preferably, this invention proposes an in-situ reaction of solid materials to prepare carbon-based silica-supported composite materials in situ. The carbon source is selected from natural plant polymers, including cellulose and hemicellulose. Cellulose is dispersed in an organic solvent, a surfactant and an alkaline solution are added, and after mechanical stirring to achieve uniform dispersion, solid-liquid separation is performed. The solid is washed with deionized water and dried under vacuum to obtain cellulose that has adsorbed the alkaline solution. The obtained solid is dispersed in an organic solution to obtain a cellulose suspension. A 0.01-0.1M tetraethyl silicate organic solution is prepared and added dropwise to the uniformly stirred cellulose suspension. A white turbidity is generated in the system. This solution is transferred to a polytetrafluoroethylene reactor and heated at 160-260°C for 1-3 hours. After naturally cooling to room temperature, the surface of the solid is ultrasonically cleaned with deionized water. The solid is then dried at a constant temperature of 60-80°C for 1-3 hours to obtain a carbon-based SiO2 composite material. This composite material is used to prepare low-VOC polymer resin. Impact-resistant PP granules, 0.2 wt% antioxidant, and 0.5-10 wt% carbon-based SiO2 composite material are mixed evenly in a high-speed mixer. The premixed mixture is added to a co-rotating twin-screw extruder and extruded and granulated at 185-210°C to obtain a composite resin material. After drying at 80°C for 1-3 hours, low-VOC PP resin is obtained.

[0050] As can be seen from the above, this invention uses carbon and silicon sources as raw materials to synthesize a composite containing carbon source (such as cellulose) and SiO2 in situ in a liquid phase system. This composite is then subjected to hydrothermal carbonization to prepare a composite component containing SiO2 and activated carbon fiber. Utilizing a carbon source dispersion system that adsorbs alkaline solution, SiO2 particles are synthesized in situ on the carbon source surface. The in-situ prepared carbon-based SiO2 composite material has a high specific surface area and superior adsorption performance. Adding it as a filler to resin can significantly improve VOC release and simultaneously enhance the impact resistance of the resin material.

[0051] A third objective of this invention is to provide an application of a carbon-based silica composite material as described in any one of the objectives of this invention, or a carbon-based silica composite material prepared by the method described in any one of the objectives of this invention, as a resin filler; preferably, as a high-impact, low-VOC resin filler; more preferably, as a high-impact, low-VOC polypropylene resin filler.

[0052] The fourth objective of this invention is to provide a high-impact, low-VOC resin composite material, wherein the filler used in the resin composite material is selected from the carbon-based silica composite material described in any one of the objectives of this invention or the carbon-based silica composite material prepared by the method described in any one of the objectives of this invention.

[0053] Preferably,

[0054] The filler content in the high-impact, low-VOC resin composite material is 0.5-10 wt%.

[0055] The fifth objective of this invention is to provide a method for preparing a high-impact, low-VOC resin composite material, wherein resin granules, antioxidants and fillers are mixed evenly and then fed into a twin-screw extruder, extruded and granulated, and dried to obtain the high-impact, low-VOC resin composite material.

[0056] The filler is selected from the carbon-based silica composite material according to any one of the objectives of this invention or the carbon-based silica composite material prepared by the method according to any one of the objectives of this invention.

[0057] The method is preferably used for the preparation of the high-impact, low-VOC resin composite material as described in the fourth objective of this invention.

[0058] In the preparation method of the high-impact, low-VOC resin composite material of the present invention, preferably,

[0059] The antioxidant is selected from at least one of antioxidant 168, antioxidant 1076, and antioxidant 1010; preferably, the antioxidant is selected from antioxidant 168 or an antioxidant compounded with at least one of antioxidant 168 and antioxidant 1076 and antioxidant 1010; and / or,

[0060] The resin granules are selected from polypropylene resin granules; and / or,

[0061] The antioxidant content in the high-impact, low-VOC resin composite material is 0.05wt%-0.2wt%; and / or,

[0062] The filler content in the high-impact, low-VOC resin composite material is 0.5-10 wt%; and / or,

[0063] The extrusion granulation temperature is 185–210℃; and / or,

[0064] The twin-screw extruder is selected from the co-rotating twin-screw extruder.

[0065] This invention utilizes a hydrothermal method to prepare a carbon-supported material, which enhances the system's adsorption capacity, increases its specific surface area, and improves its adsorption performance. This invention proposes an in-situ reaction of a solid material, synthesizing SiO2 on the surface of cellulose in situ, simultaneously preparing a cellulose-SiO2 composite material. After hydrothermal carbonization, a carbon-based SiO2 composite material is obtained. This composite material can be used to adsorb VOCs released from polymer resins, enabling the preparation of low-VOC resin composite materials. Furthermore, this composite material possesses the rigidity characteristic of inorganic materials, enhancing the impact resistance of the resin.

[0066] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values; these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In the following, various technical solutions can, in principle, be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0067] Compared with the prior art, the present invention has at least the following advantages:

[0068] This invention utilizes a carbon source (such as cellulose) dispersion system for adsorbing alkaline solutions to synthesize SiO2 particles in situ on the surface of cellulose. The carbon-based SiO2 composite material prepared in situ has a high specific surface area and excellent adsorption performance. When added to resin as a filler, it can significantly improve the VOC release of the material and at the same time improve the impact resistance of the resin material.

[0069] The carbon-based silica composite material of the present invention has the rigidity of inorganic materials, which can enhance the impact resistance of resin.

[0070] The cellulose used in this invention is characterized by its abundant sources, good biocompatibility, and stable physical and chemical properties. The carbon materials prepared using cellulose biomass as a precursor have a porous structure, are low in cost, and are environmentally friendly. They have great application prospects in environmental protection, materials science, and other fields. Attached Figure Description

[0071] Figure 1 shows the headspace-gas chromatography-mass spectrometry (HGC-MS) total ion chromatogram of volatile organic compounds in the original high-impact PP sample.

[0072] Figure 2 is the headspace-gas chromatography-mass spectrometry total ion chromatogram of volatile organic compounds of pp in Example 1;

[0073] Figure 3 is the headspace-gas chromatography-mass spectrometry total ion chromatogram of volatile organic compounds of PP in Example 2;

[0074] Figure 4 is the headspace-gas chromatography-mass spectrometry total ion chromatogram of volatile organic compounds of PP in Example 3;

[0075] Figure 5 shows the total ion chromatogram of volatile organic compounds in PP in Comparative Example 1, obtained by headspace-gas chromatography-mass spectrometry.

[0076] Figure 6 shows the headspace-gas chromatography-mass spectrometry (HGS-MS) total ion chromatogram of volatile organic compounds in pp in Comparative Example 2. Detailed Implementation

[0077] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0078] It should also be noted that the various specific technical features described in the following embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the various possible combinations will not be described separately in this invention.

[0079] Furthermore, various embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention. The resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0080] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0081] Raw material source:

[0082] In the following examples, all reagents used were commercially available chemicals of analytical grade; wherein,

[0083] The impact-resistant PP granules used are polypropylene resin granules, grade PPH-Y24.

[0084] The molecular weight of cellulose is 1.0 × 10⁻⁶. 5 .

[0085] Test method:

[0086] In the following examples, the VOCs of the materials were quantitatively determined using an Agilent 7890A-5975C gas chromatography-mass spectrometry system and a G1888A headspace sampler.

[0087] The following materials were subjected to quantitative VOC testing under the following conditions:

[0088] Headspace sampler conditions: 1.0 g sample, headspace heating temperature 120℃, holding temperature for 60 min.

[0089] Chromatographic conditions: HP-5MS gas chromatographic column (30m×0.25mm×0.25μm), programmed temperature rise.

[0090] Mass spectrometry conditions: EI ionization source, full scan, m / z 20–500.

[0091] The quantitative method uses isomeric nonane as a standard and an external standard curve is plotted for quantitative calculation.

[0092] The mechanical properties of the material are tested according to the following standards:

[0093] MFR was tested according to standard GB / T 3682.1—2018, with a temperature of 230℃ and a load of 2.16kg;

[0094] Tensile properties were tested according to standard GB / T 1040—2006, with a tensile rate of 50 mm / min;

[0095] Bending performance was tested according to standard GB / T 9341—2008;

[0096] The notched impact strength of simply supported beams was tested according to standard GB / T 1043.1—2008;

[0097] The heat distortion temperature was tested according to standard GB / T 1634.1—2004.

[0098] Example 1

[0099] Carbon-based SiO2 composite materials were prepared according to the following steps:

[0100] Step (1): Disperse 5.0g of cellulose in 20mL of ethanol, add 20mL of 5wt% sodium dodecylbenzenesulfonate surfactant aqueous solution and 20mL of 1wt% urea aqueous solution, stir thoroughly, and after stirring and dispersing evenly, soak for 3 hours, then perform solid-liquid separation, wash the solid with deionized water, and vacuum dry at 60℃ for 2 hours to obtain modified cellulose.

[0101] Step (2) Disperse the solid (modified cellulose) obtained in step 1 in 100 mL of ethanol and stir at high speed to obtain a uniformly dispersed cellulose suspension.

[0102] Step (3): Prepare an ethanol solution of TEOS (tetraethoxysilane): Disperse 0.55 mL of TEOS in 50 mL of ethanol for later use;

[0103] Step (4): Preparation of carbon-based SiO2 composite material: The ethanol solution of TEOS prepared in step 3 was slowly added dropwise to the uniformly stirred cellulose suspension prepared in step 2. After high-speed stirring, the solution was transferred to a high-pressure reactor. After reacting at 200°C for 2 hours, the mixture was cooled to room temperature, and the solid and liquid were separated. The solid was ultrasonically cleaned with deionized water.

[0104] Step (5): Dry the solid obtained in step 4 at 80°C for 2 hours to obtain carbon-based SiO2 composite material.

[0105] Low-VOC polymer resins are prepared according to the following method:

[0106] Step (6): Mix the impact-resistant PP granules, 0.2wt% 168 antioxidant and 3wt% carbon-based SiO2 composite material evenly in a high-speed mixer. Add the premixed mixture to a co-rotating twin-screw extruder and extrude and granulate at 185-210℃ to obtain PP composite resin material. Dry at 80℃ for 2 hours to obtain low VOC PP resin.

[0107] Example 2

[0108] Carbon-based SiO2 composite materials were prepared according to the following steps:

[0109] Step (1): Disperse 5.0g of cellulose in 20mL of ethanol, add 20mL of 5wt% sodium dodecylbenzenesulfonate surfactant aqueous solution and 20mL of 1wt% urea aqueous solution, stir thoroughly, and after stirring and dispersing evenly, soak for 3 hours, then perform solid-liquid separation, wash the solid with deionized water, and vacuum dry at 60℃ for 2 hours to obtain modified cellulose.

[0110] Step (2) The solid obtained in step 1 is dispersed in an ethanol solution and stirred at high speed to obtain a cellulose suspension;

[0111] Step (3): Prepare an ethanol solution of TEOS: Dissolve 1.1 mL of TEOS in 50 mL of ethanol and set aside for later use.

[0112] Step (4): Preparation of carbon-based SiO2 composite material: The ethanol solution of TEOS prepared in step 3 is slowly added dropwise to the uniformly stirred cellulose suspension prepared in step 2. After high-speed stirring, the solution is transferred to a high-pressure reactor and heated at 230°C for 1 hour. After cooling to room temperature, the solid surface is ultrasonically cleaned with deionized water.

[0113] Step (5): Dry the solid obtained in step 4 at 60°C for 1 hour to obtain carbon-based SiO2 composite material.

[0114] Low-VOC polymer resins are prepared according to the following method:

[0115] Step (6): Mix the impact-resistant PP granules, 0.2wt% antioxidant 168 and 3wt% carbon-based SiO2 composite material evenly in a high-speed mixer. Add the premixed mixture to a co-rotating twin-screw extruder and extrude and granulate at 185-210℃ to obtain PP composite resin material. Dry it at 80℃ for 2 hours to obtain low VOC PP resin.

[0116] Example 3

[0117] Carbon-based SiO2 composite materials were prepared according to the following steps:

[0118] Step (1): Disperse 5.0g of cellulose in 20mL of ethanol, add 20mL of 5wt% sodium dodecylbenzenesulfonate surfactant aqueous solution and 20mL of 1wt% NaOH aqueous solution, stir thoroughly, and after stirring and dispersing evenly, soak for 3 hours, then perform solid-liquid separation, wash the solid with deionized water, and vacuum dry at 60℃ for 2 hours to obtain modified cellulose.

[0119] Step (2) Disperse the solid obtained in step 1 in 100 mL of ethanol solution and stir at high speed to obtain a cellulose suspension;

[0120] Step (3): Prepare an ethanol solution of TEOS: Dissolve 0.22 mL of TEOS in 50 mL of ethanol for later use.

[0121] Step (4): Preparation of carbon-based SiO2 composite material: The ethanol solution of TEOS prepared in step 3 is slowly added dropwise to the cellulose suspension prepared in step 2 and stirred at high speed. After stirring at high speed, the solution is transferred to a high-pressure reactor and heated at 200°C for 1 hour. After cooling to room temperature, the solid surface is ultrasonically cleaned with deionized water.

[0122] Step (5): Dry the solid obtained in step 4 at 80°C for 1 hour to obtain carbon-based SiO2 composite material.

[0123] Low-VOC polymer resins are prepared according to the following method:

[0124] Step (6): Mix the impact-resistant PP granules, 0.2wt% antioxidant 168 and 3wt% carbon-based SiO2 composite material evenly in a high-speed mixer. Add the premixed mixture to a co-rotating twin-screw extruder and extrude and granulate at 185-210℃ to obtain PP composite resin material. Dry it at 80℃ for 2 hours to obtain low VOC PP resin.

[0125] The composition of the carbon-based silica composite material prepared in the embodiments of the present invention was obtained by X-ray fluorescence elemental analysis, as shown in Table 1 below.

[0126] Table 1. Composition of carbon-based silica composite materials

[0127] The mass ratio of activated carbon fiber to silica in the examples is as follows: Example 16:1, Example 22:1, Example 39:1 surface

[0128] Comparative Example 1

[0129] Carbon-based SiO2 composite materials were prepared according to the following steps:

[0130] Step (1): Disperse 5.0g of cellulose in 20mL of ethanol, add 20mL of 5wt% sodium dodecylbenzenesulfonate surfactant aqueous solution and 20mL of 1wt% NaOH aqueous solution, stir thoroughly and disperse evenly, soak for 3 hours, then perform solid-liquid separation, wash the solid with deionized water, and vacuum dry at 60℃ for 2 hours to obtain modified cellulose;

[0131] Step (2): Disperse the solid obtained in step 1 in 100 mL of ethanol solution and stir at high speed to obtain a cellulose suspension;

[0132] Step (3): The cellulose suspension prepared in step 2 was transferred to a high-pressure reactor and heated at 200°C for 1 hour. After cooling to room temperature, the solid surface was ultrasonically cleaned with deionized water to obtain carbonized cellulose. SiO2 (the SiO2 prepared in Comparative Example 3 below) was added at a mass ratio of 9:1 between carbonized cellulose and silicon dioxide and mechanically mixed to obtain a carbon-based SiO2 composite material.

[0133] Low-VOC polymer resins are prepared according to the following method:

[0134] Step (4): Mix the impact-resistant PP granules, 0.2wt% 168 antioxidant and 3wt% carbon-based SiO2 composite material evenly in a high-speed mixer. Add the premixed mixture to a co-rotating twin-screw extruder and extrude and granulate at 185-210℃ to obtain PP composite resin material. Dry it at 80℃ for 2 hours to obtain low VOC PP resin.

[0135] Comparative Example 2

[0136] Carbon-based materials are prepared according to the following steps:

[0137] Step (1): Disperse 5.0g of cellulose in 20mL of ethanol, add 20mL of 5wt% sodium dodecylbenzenesulfonate surfactant aqueous solution and 20mL of 1wt% NaOH aqueous solution, stir and mix thoroughly, soak for 3 hours, then perform solid-liquid separation, wash the solid with deionized water, and vacuum dry at 60℃ for 2 hours to obtain modified cellulose.

[0138] Step (2): Disperse the solid obtained in step 1 in 100 mL of ethanol solution and stir at high speed to obtain a cellulose suspension;

[0139] Step (3): Transfer the cellulose suspension from step 2 to a high-pressure reactor, heat it at 200°C for 1 hour, cool it to room temperature, ultrasonically clean the solid surface with deionized water, and dry it at 80°C for 1 hour to obtain carbon-based material.

[0140] Low-VOC polymer resins are prepared according to the following method:

[0141] Impact-resistant PP granules, 0.2 wt% antioxidant 168, and 3 wt% carbon-based materials are mixed evenly in a high-speed mixer. The premixed mixture is then added to a co-rotating twin-screw extruder and extruded and granulated at 185–210°C to obtain PP composite resin material. The PP resin is then dried at 80°C for 2 hours.

[0142] Comparative Example 3

[0143] Step (1): Prepare an ethanol solution of TEOS: Dissolve 0.22 mL of TEOS in 50 mL of ethanol for later use.

[0144] Step (2): Preparation of SiO2 material: Transfer the ethanol solution of TEOS prepared in step (1) and 1000 mL of ethanol to a high-pressure reactor, heat and react at 200°C for 1 hour, cool to room temperature, and ultrasonically clean the solid surface with deionized water.

[0145] Step (3): Dry the solid obtained in step (2) at 80°C for 1 hour to obtain SiO2 material.

[0146] Low-VOC polymer resins are prepared according to the following method:

[0147] Impact-resistant PP granules, 0.2 wt% antioxidant 168, and 3 wt% SiO2 material are mixed evenly in a high-speed mixer. The premixed mixture is added to a co-rotating twin-screw extruder and extruded and granulated at 185–210°C to obtain PP composite resin material. The PP resin is then dried at 80°C for 2 hours.

[0148] The VOC test and quantitative calculation results of the resin composite materials prepared in the embodiments and comparative examples of the present invention are shown in Table 2 below. The specific headspace-gas chromatography-mass spectrometry total ion chromatograms of volatile organic compounds are shown in Figures 1, 2, 3, 4, 5 and 6.

[0149] Table 2. VOC test and quantitative calculation results for all samples

[0150]

[0151] The mechanical property test results of the resin composite materials prepared in the embodiments and comparative examples of the present invention are shown in Table 3 below.

[0152] Table 3. Test results of mechanical properties of the samples

[0153]

[0154] By comparing the results of Example 3 and Comparative Example 1, it can be seen that only by synthesizing the composite containing carbon source and SiO2 in situ in this invention, and then undergoing hydrothermal carbonization, can the composite component containing SiO2 and activated carbon fiber be prepared with superior adsorption performance. Adding it as a filler to the resin can more significantly improve the VOC release of the material and better improve the impact resistance of the resin material.

[0155] By comparing the results of Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3, it can be seen that the composite components containing SiO2 and activated carbon fiber prepared by the method of the present invention have a synergistic effect. The two components have better adsorption performance when used together. When they are added to the resin as fillers, the VOC release of the material can be improved more significantly, and the impact resistance of the resin material can be improved better.

[0156] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

[0157] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0158] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0159] In the context of this specification, except where expressly stated otherwise, any matters or issues not mentioned shall apply directly to those known in the art without any modification.

Claims

1. A high-impact, low-VOC resin composite material, characterized in that: The filler used in the resin composite material is a carbon-based silica composite material; the carbon-based silica composite material is a carbon-based silica composite material with silica loaded on the surface of activated carbon fiber; the mass ratio of activated carbon fiber to silica in the carbon-based silica composite material is 10:1~2:1; the preparation method of the carbon-based silica composite material includes the following steps: (1) after mixing the organic solvent dispersion of carbon source, surfactant solution and alkali solution evenly, soaking, solid-liquid separation, washing solid, and vacuum drying to obtain modified carbon source; the carbon source is selected from at least one of cellulose and hemicellulose; (2) the modified carbon source is evenly dispersed in organic solvent to obtain suspension; (3) silicon source solution is added to suspension, and after being evenly dispersed, hydrothermal carbonization reaction is carried out in high pressure reactor to obtain carbon-based silica composite material; the silicon source solution is selected from organic solution of alkoxysilane.

2. The high-impact, low-VOC resin composite material according to claim 1, characterized in that: In step (1), the surfactant in the surfactant solution is selected from at least one of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium fatty alcohol sulfate, and sodium succinate sulfonate; and / or, the alkali in the alkaline solution is selected from at least one of sodium hydroxide, potassium hydroxide, urea, and ammonia; and / or, the organic solvent in the organic solvent dispersion of the carbon source is selected from at least one of ethanol, acetone, tetrahydrofuran, and ethyl acetate.

3. The high-impact, low-VOC resin composite material according to claim 2, characterized in that: The molecular weight of the carbon source is 0.5 × 10⁻⁶. 4 ~2.0×10 5 .

4. The high-impact, low-VOC resin composite material according to claim 1, characterized in that: In step (1), the mass ratio of the carbon source to the surfactant is 1:1 to 100:1; and / or, the mass ratio of the carbon source to the alkali in the alkaline solution is 200:1 to 4:1; and / or, the soaking time is 1-5 hours.

5. The high-impact, low-VOC resin composite material according to claim 4, characterized in that: The concentration of the surfactant solution is 0.5wt-20wt%; and / or the concentration of the alkali solution is 0.1wt%-5wt%.

6. The high-impact, low-VOC resin composite material according to claim 1, characterized in that: In step (2), the organic solvent is selected from at least one of ethanol, acetone, tetrahydrofuran, and ethyl acetate; and / or the mass ratio of the modified carbon source to the organic solvent is 1:10 to 1:

2.

7. The high-impact, low-VOC resin composite material according to claim 1, characterized in that: In step (3), the alkoxysilane in the silicon source solution is selected from at least one of tetraethyl silicate and tetramethyl orthosilicate; and / or, the organic solvent in the silicon source solution is selected from at least one of ethanol, acetone, tetrahydrofuran, and ethyl acetate; and / or, the concentration of the silicon source solution is 0.5 wt% to 10 wt%; and / or, the mass ratio of the alkoxysilane in the carbon source and silicon source solutions is 40:1 to 4.5:

1.

8. The high-impact, low-VOC resin composite material according to claim 1, characterized in that: In step (3), a silicon source solution is added dropwise to the suspension; and / or, the temperature of the hydrothermal carbonization reaction is 160-260℃; and / or, the time of the hydrothermal carbonization reaction is 1-3 hours.

9. A high-impact, low-VOC resin composite material as described in claim 1, characterized in that, The filler content in the high-impact, low-VOC resin composite material is 0.5-10 wt%.

10. A method for preparing a high-impact, low-VOC resin composite material as described in any one of claims 1-9, characterized in that, The resin granules, antioxidants and fillers are mixed evenly, extruded and granulated, and dried to obtain the high-impact, low-VOC resin composite material.

11. The method for preparing the high-impact, low-VOC resin composite material according to claim 10, characterized in that, The antioxidant is selected from at least one of antioxidant 168, antioxidant 1076, and antioxidant 1010; and / or, the resin granules are selected from polypropylene resin granules; and / or, the antioxidant content in the high-impact, low-VOC resin composite material is 0.05 wt%-0.2 wt%; and / or, the filler content in the high-impact, low-VOC resin composite material is 0.5-10 wt%; and / or, the extrusion granulation temperature is 185-210 ℃; and / or, the extrusion granulation is performed using a twin-screw extruder.

12. The method for preparing the high-impact, low-VOC resin composite material according to claim 11, characterized in that, The antioxidant is selected from antioxidant 168; the twin-screw extruder is selected from co-rotating twin-screw extruder.

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