WO2023241196A1 - Preparation of graphene/natural rubber with simultaneously improved mechanical property, heat conduction and wear resistance - Google Patents

Preparation of graphene/natural rubber with simultaneously improved mechanical property, heat conduction and wear resistance Download PDF

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WO2023241196A1
WO2023241196A1 PCT/CN2023/088343 CN2023088343W WO2023241196A1 WO 2023241196 A1 WO2023241196 A1 WO 2023241196A1 CN 2023088343 W CN2023088343 W CN 2023088343W WO 2023241196 A1 WO2023241196 A1 WO 2023241196A1
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graphene
natural rubber
rubber
graphene oxide
silica
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PCT/CN2023/088343
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French (fr)
Chinese (zh)
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刘亚青
赵贵哲
龚明山
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中北大学
山西中北新材料科技有限公司
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Publication of WO2023241196A1 publication Critical patent/WO2023241196A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2307/00—Characterised by the use of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers

Definitions

  • the invention belongs to the field of natural rubber composite materials, and is specifically a preparation method of graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties.
  • Natural rubber has a series of excellent physical properties, such as good resilience, insulation, tear resistance, plasticity, etc., and is widely used in many fields. Although NR has self-reinforcing properties, it still cannot meet the usage requirements, resulting in limited applications in some fields.
  • Graphene and its derivatives have extremely excellent physical and chemical properties and can significantly improve the mechanical properties, thermal properties, conductive properties, etc. of the polymer matrix.
  • Graphene oxide (GO) is a two-dimensional (2D) material with a variety of oxygen-containing functional groups obtained by oxidizing graphite through physical and chemical means. It is an economical way to mass-produce graphene oxide.
  • the surface of GO contains a large number of oxygen-containing functional groups, which can react with many functional groups, so that graphene oxide can be easily compounded with other functional particles.
  • Silica also known as white carbon black, has become the best rubber reinforcing filler to replace carbon black due to its smaller particle size and more surface functional groups. Adding silica to the rubber matrix improves the mechanical properties of rubber composites and reduces rolling resistance.
  • the present invention aims to provide a preparation method of graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties.
  • the invention is realized through the following technical solutions: a graphene/graphene/ A method for preparing natural rubber, wherein silica and graphene oxide form graphene oxide loaded with nano-silica through electrostatic interaction, and then the graphene oxide loaded with nano-silica is added to natural rubber latex, using water
  • the graphene masterbatch is prepared through a synergistic coagulation process, and graphene/natural rubber is further obtained through a mechanical blending method and a vulcanization process.
  • the present invention utilizes an aqueous phase cooperative coagulation process and a mechanical blending method to uniformly disperse graphene oxide loaded with silica through electrostatic interaction in natural rubber vulcanized rubber, and the electrostatic interaction between silica and graphene oxide
  • the effect is a dynamic force that not only strengthens the cross-linked network structure of the graphene/natural rubber composite and greatly increases the cross-link density, but also enables the graphene filler to entangle a large amount of rubber during the dynamic movement of the rubber.
  • the molecular chain enhances the interfacial interaction between graphene and the rubber matrix, thereby obtaining a graphene/natural rubber vulcanized rubber with improved mechanical, thermal conductivity and wear resistance properties.
  • the invention further provides a preparation method of graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties, including the following steps:
  • step (1) water and ethanol are prepared in a volume ratio of 1:1-3; the dosage of the silane coupling agent KH550 is 5-5% of the mass of silica. 15%; reaction temperature is 65-85°C, reaction time is 4-8h; drying temperature is 50-70°C.
  • step (1) the concentration of amination-modified silica powder in deionized water is 50-300 mg/mL, and the concentration of citric acid solution is 1.5-4 mol/L.
  • step (1) the solubility of the graphene oxide aqueous dispersion is 0.5-10 mg/mL.
  • step (1) the mass ratio of amination-modified silica powder and citric acid is 1-3:0.5-1; the obtained silica is loaded by electrostatic interaction
  • the mass ratio of graphene oxide to silicon dioxide in graphene oxide is 1:10-60.
  • step (1) the power of ultrasonic dispersion is 50-300W.
  • step (2) deionized water is added to the natural rubber latex so that the concentration of the natural rubber latex emulsion is 10-40wt.%, the concentration of the flocculant is 10wt.%, and the flocculation
  • the mass ratio of agent to natural rubber is 2-6:100.
  • step (3) the mass ratio of the antioxidant, antioxidant, activator, softener, vulcanization accelerator, and vulcanizing agent is 1:1:5:2:2 :2.
  • the natural rubber used is 100 parts by mass, and the graphene oxide loaded with silica through electrostatic interaction is 0.5-30 parts.
  • the mass parts and rubber additives are 11-13 mass parts.
  • the present invention has the following beneficial effects:
  • the present invention adopts an efficient, simple, and easy-to-industrial production aqueous synergistic coagulation process to prepare graphene masterbatch.
  • the aqueous synergistic coagulation process can enable the prepared masterbatch to maintain excellent properties of each component in the evenly mixed emulsion.
  • the dispersion effect is good, so the graphene in the obtained masterbatch is well dispersed; in addition, the mechanical blending method is further used to make the graphene oxide loaded with silica through electrostatic interaction more uniformly dispersed in the natural rubber vulcanizate, which is the final result.
  • the graphene/natural rubber vulcanized rubber with improved mechanical, thermal conductivity and wear resistance properties lays the foundation for the process.
  • the present invention forms an electrostatic interaction between silica and graphene oxide, and the electrostatic interaction between silica and graphene oxide is a dynamic interaction, which not only enables graphene/natural rubber composite
  • the cross-linked network structure of the material is enhanced and the cross-link density is greatly increased.
  • the graphene filler can entangle a large number of rubber molecular chains and enhance the interfacial interaction between graphene and the rubber matrix.
  • the preparation process of the present invention is simple, green and environmentally friendly, without any harsh requirements, and involves conventional equipment. Therefore, it is easy for industrial production and is of great significance for promoting the application of graphene in the field of high-performance rubber.
  • Figure 1 is the infrared spectrum of silica and KH550 modified silica in Example 1 and Comparative Example 2 of the present invention.
  • Figure 2 is a potential diagram of a graphene oxide aqueous dispersion that supports silica through electrostatic interaction and a potential diagram of graphene oxide in Example 1 of the present invention.
  • Figure 3 shows (a) XPS full spectrum of GO and SiO 2 -GO prepared in Comparative Example 2, (b) C 1s peak fitting diagram of GO, (c) C 1s peak fitting of SiO 2 -GO Figure and (d) N 1s peak fitting diagram of SiO 2 -GO.
  • Figure 4 shows the XRD spectrum of GO loaded with nano-SiO 2 using different forces and the interlayer spacing d of GO calculated by the Bragg equation.
  • Figure 5 is a torque diagram of the natural rubber composite materials prepared in Example 1, Comparative Example 1 and Comparative Example 2.
  • Figure 6 shows (a) cross-linking density and (b) binder content of natural rubber vulcanized rubber prepared in Example 1, Comparative Example 1 and Comparative Example 2.
  • Figure 7 is a schematic diagram of the morphology of silica loaded on the surface of graphene oxide due to a large number of oxygen-containing functional groups.
  • the invention provides a method for preparing graphene/natural rubber with improved mechanical, thermal conductivity and wear resistance properties.
  • the electrostatic interaction between silica and graphene oxide forms graphene oxide loaded with nano-silica, and then the graphene oxide loaded with nano-silica is added to the natural latex, and the water phase is used to synergistically polymerize
  • the graphene masterbatch is prepared by the precipitation process, and graphene/natural rubber is further obtained through mechanical blending and vulcanization processes.
  • the invention further provides a preparation method of graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties, including the following steps:
  • the present invention also provides the relevant preparation mechanism of the above preparation method:
  • the ethoxy groups contained in the KH550 silane coupling agent will be hydrolyzed into hydroxyl groups, and the intermediate product is silanol.
  • the hydroxyl groups in the silanol and the hydroxyl groups on the surface of the silica undergo a dehydration condensation reaction, thereby causing the silanol to form.
  • the surface of silicon oxide is grafted with other functional groups, and then with the assistance of ultrasound, the amino groups grafted on the surface of silicon dioxide are protonated under acidic conditions.
  • the relevant reaction mechanism is as follows.
  • step (1) water and ethanol are prepared in a volume ratio of 1:1-3; the dosage of the silane coupling agent KH550 is 5-15% of the mass of silica; the reaction temperature is 65- 85°C, reaction time is 4-8h; drying temperature is 50-70°C.
  • the water and ethanol prepare a blend solution according to the volume ratio of 1:3; the dosage of the silane coupling agent KH550 is 10-12% of the mass of silica; the reaction temperature is 70-80°C, and the reaction time is 5-7h; drying temperature is 70°C.
  • step (1) the concentration of amination-modified silica powder in deionized water is 50-300 mg/mL, and the concentration of citric acid solution is 1.5-4 mol/L.
  • step (1) the solubility of the graphene oxide aqueous dispersion is 0.5-10 mg/mL.
  • step (1) the mass ratio of aminated modified silica powder and citric acid is 1-3:0.5-1; the obtained graphene oxide loading silica through electrostatic interaction is oxidized The mass ratio of graphene to silica is 1:10-60.
  • the power of ultrasonic dispersion is 50-300W.
  • step (2) deionized water is added to the natural rubber latex so that the concentration of the natural rubber latex emulsion is 10-40wt.%, the concentration of the flocculant is 10wt.%, and the mass ratio of the flocculant to the natural rubber is 2-6:100.
  • the flocculant is at least one of calcium chloride solution, sodium chloride solution, potassium chloride solution, sodium sulfate solution, hydrochloric acid solution and formic acid solution.
  • step (3) the mass ratio of the antioxidant, antioxidant, activator, softener, vulcanization accelerator, and vulcanizing agent is 1:1:5:2:2:2.
  • the natural rubber used is 100 parts by mass, and the graphene oxide loaded with silica through electrostatic interaction is 0.5-30 parts by mass. parts and rubber additives are 11-13 parts by mass.
  • the vulcanization accelerator is N-tert-butyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide Amide or N-(diethylene oxide)-2-benzothiazole sulfenamide;
  • the vulcanizing agent is sulfur or sulfur monochloride;
  • the antioxidant is 2,6-di-tert-butyl-4-methylphenol, 2,2,4-trimethyl-1,2-dihydroquinoline polymer or 2 -Thiobenzoimidazole;
  • the antioxidant is N-isopropyl-N'-phenyl-p-phenylenediamine, p-phenylaniline or dilauryl sulfide dipropionate;
  • the activator is zinc glucate, zinc oxide or Magnesium oxide; softener is stearic acid, dibutyl titanate or dioctyl adipate.
  • the mixing temperature of the internal mixer is 105-120°C, the mixing time is 3-5 minutes; the mixing temperature is 50-70°C, and the mixing time is 8 -12min; the storage time of the mixed rubber is 18-36h; the vulcanization temperature is 135-170°C, the vulcanization pressure is 10-30MPa, and the vulcanization time is 10-25min.
  • a preparation method of graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties including the following steps:
  • silane coupling agent KH550 weigh 11g of silane coupling agent KH550, add it to a blended solution of 33g of deionized water and 66g of ethanol, stir ultrasonically for 15 minutes and then continue mechanical stirring for 45 minutes to fully hydrolyze KH550. Weigh 100g of silica and add it to 100ml of a solution with a ratio of ethanol to distilled water of 3:1. After ultrasonic dispersion at 100w for 30 minutes, add the prepared silane coupling agent hydrolyzate, react at 75°C for 6 hours, filter and wash with 70 °C to constant weight to obtain aminated silica powder, expressed as m-SiO 2 .
  • step (3) Add the amino protonated silica dispersions of different masses prepared in step (1) to the 250 mL graphene oxide dispersion obtained in step (2), and disperse it ultrasonically for 15 minutes at room temperature to obtain the dielectric loaded by electrostatic interaction.
  • the aqueous dispersion of graphene oxide of silicon oxide is expressed as SiO 2 -NH 3 + /GO.
  • the specific mass of the raw materials silica and graphene oxide is shown in Table 1.
  • the prepared graphene oxide (SiO 2 -NH 3 + /GO) dispersion loaded with silica through electrostatic interaction was thoroughly stirred and mixed to obtain a uniformly dispersed mixed emulsion; 25g of 10wt.% CaCl 2 solution of flocculant was added , therefore, the modified graphene oxide particles and rubber particles gather in an orderly manner in the water phase and precipitate cooperatively; the obtained raw rubber is washed with water, removed from the water, and dried in an oven at 65°C to a constant weight, and then the result obtained by electrostatic Interaction-loaded silica-loaded graphene oxide/natural rubber masterbatch.
  • step (4) Use the graphene oxide/natural rubber masterbatch obtained in step (4) to load silica through electrostatic interaction. Place it in an internal mixer and mix at 110°C and 40 rpm. During this period, add 1g of antioxidant 4010NA, 1g of antioxidant RD, 5g of activator ZnO, and 2g of softener SA in three batches. Mix for 4 minutes each time and discharge the rubber material. . After the rubber material is cooled to room temperature, transfer it to the open mill and start mixing at 60°C. After evenly dispersed, add 2g of vulcanization accelerator NOBS and 2g of sulfur. After mixing evenly, mix until the rubber material has no bubbles.
  • the mixed rubber was vulcanized for a certain period of time (t C90 ) at 150°C and 15 MPa in a vulcanizer to obtain a multi-performance simultaneously optimized natural rubber vulcanized rubber, in which t C90 was measured by a rubber processing analyzer (RPA).
  • RPA rubber processing analyzer
  • the subsequent graphene oxide/natural rubber masterbatch and vulcanized rubber preparation processes are exactly the same as steps (4) and (5) in Example 1-4.
  • the only difference is that the graphene oxide/natural rubber masterbatch and vulcanized rubber preparation process in Example 1-4 are loaded by electrostatic interaction.
  • the graphene oxide (SiO 2 -NH 3 + /GO) dispersion of silicon dioxide is replaced with a GO (SiO 2 /GO) dispersion that supports SiO 2 through hydrogen bonds.
  • step (3) Add the protonated silica dispersion prepared in step (1) to the 250 mL graphene oxide dispersion obtained in step (2), ultrasonically disperse it at room temperature for 15 minutes, and then add a certain concentration of N-hydroxysmber dropwise Imide solution, stir magnetically for 30 minutes, slowly add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide solution dropwise, stir magnetically under ice bath conditions for 24h, and prepare by chemical Binding force-loaded SiO 2 aqueous dispersion of GO.
  • Table 1 The specific masses of silica and graphene oxide are shown in Table 1.
  • the subsequent graphene oxide/natural rubber masterbatch and vulcanized rubber preparation processes are exactly the same as steps (4) and (5) in Example 1-4.
  • the only difference is that the graphene oxide/natural rubber masterbatch and vulcanized rubber preparation process in Example 1-4 are loaded by electrostatic interaction.
  • the graphene oxide (SiO 2 -NH 3 + /GO) dispersion of silicon dioxide is replaced with a GO (SiO 2 -GO) dispersion that supports SiO 2 through chemical binding force.
  • Examples 1 to 4 The difference from Examples 1 to 4 is that no nano-silica is added and it is a graphene oxide/natural rubber composite material, that is, steps (1), (2) and (3) in the preparation process of Examples 1 to 4 are not included. ), which are exactly the same as steps (4) and (5) in Example 1-4, that is, graphene oxide (SiO 2 -NH 3 + /GO) loaded with silica through electrostatic interaction in Example 1-4 The dispersion liquid was replaced with GO dispersion liquid.
  • the performance test standards are as follows:
  • the IS50 Fourier transform infrared spectrometer of American Thermoelectric Company was used to conduct functional group analysis on SiO 2 and m-SiO 2.
  • the test range was 500-4000cm -1 .
  • the test method was to grind the sample and KBr powder at a ratio of 1:100 and mix them evenly. , pressed into thin slices.
  • 3410cm -1 is attributed to the hydroxyl-OH stretching vibration on the SiO 2 surface.
  • the symmetric stretching vibration peaks of Si-O-Si unique to SiO 2 are at 795cm -1 and 1066cm -1 corresponding to Si-O- The antisymmetric stretching vibration peak of Si. It can be clearly seen from the infrared spectrum of m-SiO 2 that the in-plane deformation vibration peak of NH in -NH 2 at 1633cm -1 and the unique stretching vibration peak of CH at 2930cm -1 indicate that the silane coupling Joint agent KH550 successfully modified SiO 2 .
  • the Dandongfang Yuan DX-2700B X-ray diffraction analyzer was used to test and analyze the crystal structures of GO, SiO 2 /GO, SiO 2 -NH 3 + /GO and SiO 2 -GO through X-rays radiated by Cu-K ⁇ .
  • the scanning angle is 5-80°
  • the sampling time is 0.2s
  • the step angle is 0.03°.
  • Figure 2 clearly shows the zeta potential diagrams of GO and SiO 2 -NH 3+ . It is clear from the figure that after the modified SiO 2 is treated with citric acid, the amino groups grafted on the surface are protonated by the acid, making the diluted silica dispersion positively charged, and measured by a Zeta potential analyzer. Obtained, the potential of SiO 2 dispersion is +43mv. However, the potential of the graphene oxide dispersion was -40mv as measured by a Zeta potential analyzer.
  • the NEXSA X-ray photoelectron spectrometer analyzer from Thermo Fisher Company in the United States was used to test and analyze changes in surface elements and chemical compositions of GO and SiO 2 -GO.
  • the test scan is in CAE mode, the pass of full spectrum scan is 160eV, and the pass of narrow spectrum scan is 40eV.
  • Figure 3(a) shows the full XPS spectrum of GO and SiO 2 -GO prepared in Comparative Example 2. It can be clearly seen from the figure that the XPS full spectrum of SiO 2 -GO has the characteristic Si 2s and Si 2p peaks of Si, as well as the characteristic N 1s peak.
  • Figure 3(c) a new CN peak appears at 285.8eV, indicating that the amidation reaction between the oxygen-containing functional groups on the surface of graphene oxide and the amino group on the surface of SiO 2 has occurred.
  • the RPA-8000 rubber processing analyzer of Taiwan High Speed Rail Corporation was used to analyze the vulcanization characteristics of the rubber compound.
  • the test conditions are to weigh 3-5g of the mixed rubber, cover both sides with cellophane paper, place it on a rotor with a temperature of 150°C, and measure the optimal vulcanization time and corresponding torque value.
  • the graphene/natural rubber prepared in Example 1 has the largest torque difference, indicating that the composite material has the largest cross-linked network structure between graphene and the natural rubber matrix. This is mainly Since the electrostatic force is a reversible force, the network structure of the entire composite system is enhanced, thus macroscopically manifesting as the largest torque difference of GO/SiO 2 -NH 3 + /NR.
  • Figure 5(b) is a strain scan of the rubber composite material, which shows that there are electrostatic interactions between graphene oxide layers. When used, that is, the graphene/natural rubber composite material prepared in Example 1 has the best dispersion effect of the filler in the rubber matrix.
  • V r is the volume fraction of rubber in the equilibrium swelling material
  • ⁇ is the mass fraction of rubber in the sample
  • ⁇ is the mass loss rate of the sample during the swelling process
  • ⁇ r is the density of the rubber composite material
  • ⁇ s is the density of the solvent toluene.
  • V e is the cross-linking density of rubber
  • V s is the molar volume of solvent toluene
  • ⁇ is the solvent interaction parameter between rubber and toluene.
  • a differential scanning calorimeter was used to test and analyze the binder content of rubber composite materials. All test conditions were carried out at temperatures between -80°C and 25°C, with a heating rate of 5°C/min.
  • ⁇ C p is the heat capacity jump of the rubber at the glass transition temperature
  • ⁇ C pn is the normalized value of the heat tolerance of the rubber composite when filled with fillers
  • w is the weight fraction of the filler in the rubber composite
  • ⁇ C p0 is the jump heat capacity at the glass transition temperature of the unfilled rubber matrix
  • ⁇ im is the binder content.
  • Figure 6(a) shows that when the same amount of graphene oxide is added, when there is an electrostatic force between the GO layers, that is, the cross-linking density of the rubber composite prepared by the present invention is much greater than the hydrogen bonds between the layers (Comparative Example 1) Cross-link density of rubber composites combined with chemical bonds (Comparative Example 2).
  • Figure 6(b) shows that compared to the presence of hydrogen bonds (Comparative Example 1) and chemical bond forces (Comparative Example 2) between GO layers, when there are electrostatic forces between GO layers (the present invention), the prepared graphene/ In rubber composites, the proportion of rubber molecular chains anchored by graphene is much larger. This also intuitively shows that the electrostatic force between GO layers is a reversible force.
  • the filler can entangle a large number of rubber molecular chains to a large extent and make the interface between the filler and the rubber matrix interact with each other. Enhanced effect.
  • the testing standard for thermal conductivity is GB/T3399
  • the testing standard for abrasion performance is GB/T9867-2008
  • the testing standard for mechanical properties is ISO37-2005
  • the tensile rate is 500mm/min
  • the tearing speed is 500mm/min.

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Abstract

A method for preparing graphene/natural rubber with simultaneously improved mechanical property, heat conduction and wear resistance, comprising: forming graphene oxide loaded with nano silicon dioxide by means of electrostatic interaction between silicon dioxide and graphene oxide; adding graphene oxide loaded with nano silicon dioxide into natural latex; preparing a graphene master batch by using an aqueous phase synergistic coagulation process; and obtaining graphene/natural rubber by means of a mechanical blending method and a vulcanization process. The electrostatic interaction between silicon dioxide and graphene oxide is a dynamic acting force which not only reinforces the crosslinked network structure of the graphene/natural rubber composite material and significantly increases the crosslinking density, but also enables the graphene filler to entangle a large amount of rubber molecular chains and enhances the interface interaction between the graphene and the rubber matrix in the dynamic movement process of the rubber, thereby improving the mechanical property, the heat conduction and the wear resistance simultaneously.

Description

力学、导热和耐磨性同时提升的石墨烯/天然橡胶的制备Preparation of graphene/natural rubber with improved mechanical properties, thermal conductivity and wear resistance 技术领域Technical field
本发明属于天然橡胶复合材料领域，具体是一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法。The invention belongs to the field of natural rubber composite materials, and is specifically a preparation method of graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties.
背景技术Background technique
天然橡胶(NR)具有一系列优异的物理性能，如良好的回弹性、绝缘性、抗撕裂、可塑等，被广泛应用于多个领域。NR虽具有自补强的特性，但仍不能满足使用要求，导致在某些领域的应用受限。Natural rubber (NR) has a series of excellent physical properties, such as good resilience, insulation, tear resistance, plasticity, etc., and is widely used in many fields. Although NR has self-reinforcing properties, it still cannot meet the usage requirements, resulting in limited applications in some fields.
石墨烯及其衍生物具有极为优异的物理化学性能，可显著提高聚合物基体的力学性能、热性能、导电性能等。氧化石墨烯(GO)是通过物理化学等手段对石墨进行氧化而得到的一种带有多种含氧官能团的二维(2D)材料，是大批量生产氧化石墨烯的经济途径。GO表面含有大量的含氧官能团，它们能够与很多官能团反应，从而使氧化石墨烯可以很方便与其它功能粒子复配。二氧化硅，又名白炭黑，由于其较小的粒径以及较多的表面官能团，成为替代炭黑的最优橡胶补强填料。添加二氧化硅至橡胶基体中可以提高橡胶复合材料的机械性能并降低滚动阻力。Graphene and its derivatives have extremely excellent physical and chemical properties and can significantly improve the mechanical properties, thermal properties, conductive properties, etc. of the polymer matrix. Graphene oxide (GO) is a two-dimensional (2D) material with a variety of oxygen-containing functional groups obtained by oxidizing graphite through physical and chemical means. It is an economical way to mass-produce graphene oxide. The surface of GO contains a large number of oxygen-containing functional groups, which can react with many functional groups, so that graphene oxide can be easily compounded with other functional particles. Silica, also known as white carbon black, has become the best rubber reinforcing filler to replace carbon black due to its smaller particle size and more surface functional groups. Adding silica to the rubber matrix improves the mechanical properties of rubber composites and reduces rolling resistance.
力学性能是橡胶交联网络构建和填料分散状况的直接反映。在动态载荷的作用下，更强的交联网络会限制填料，阻止橡胶大分子链从填料表面滑落。橡胶的磨损与其本身的抵抗、力学性能、填料网络结构和交联网状结构相关。因此，构建更完善的交联网络是实现橡胶性能提升的关键。获得具有优异力学性能的复合材料能够扩大橡胶的应用范围，而优异的导热性能可以降低橡胶使用过程的热量累积，优异的耐磨损性能能够提高橡胶的使用寿命。Mechanical properties are a direct reflection of the rubber cross-linked network construction and filler dispersion conditions. Under dynamic load, a stronger cross-linked network will constrain the filler and prevent the rubber macromolecular chains from sliding off the filler surface. The wear of rubber is related to its own resistance, mechanical properties, filler network structure and cross-linked network structure. Therefore, building a more complete cross-linked network is the key to improving rubber performance. Obtaining composite materials with excellent mechanical properties can expand the application range of rubber, while excellent thermal conductivity can reduce heat accumulation during rubber use, and excellent wear resistance can increase the service life of rubber.
发明内容Contents of the invention
本发明旨在提供一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法。The present invention aims to provide a preparation method of graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties.
本发明是通过以下技术方案实现的：一种力学、导热和耐磨性能同时提升的石墨烯/ 天然橡胶的制备方法，其中二氧化硅与氧化石墨烯之间通过静电相互作用形成负载纳米二氧化硅的氧化石墨烯，然后将负载纳米二氧化硅的氧化石墨烯加入到天然胶乳中，利用水相协同聚沉工艺制备得到石墨烯母胶，并进一步通过机械共混法和硫化工艺得到石墨烯/天然橡胶。The invention is realized through the following technical solutions: a graphene/graphene/ A method for preparing natural rubber, wherein silica and graphene oxide form graphene oxide loaded with nano-silica through electrostatic interaction, and then the graphene oxide loaded with nano-silica is added to natural rubber latex, using water The graphene masterbatch is prepared through a synergistic coagulation process, and graphene/natural rubber is further obtained through a mechanical blending method and a vulcanization process.
本发明利用水相协同聚沉工艺以及机械共混法能够使通过静电相互作用负载二氧化硅的氧化石墨烯均匀分散在天然橡胶硫化胶中，而二氧化硅与氧化石墨烯之间的静电相互作用是一种动态作用力，不仅能够使石墨烯/天然橡胶复合材料的交联网络结构增强、交联密度大幅增加，而且在橡胶动态运动的过程中，能够使石墨烯填料缠结大量的橡胶分子链且使石墨烯与橡胶基体间的界面相互作用增强，从而得到力学、导热和耐磨性能同时提升的石墨烯/天然橡胶硫化胶。The present invention utilizes an aqueous phase cooperative coagulation process and a mechanical blending method to uniformly disperse graphene oxide loaded with silica through electrostatic interaction in natural rubber vulcanized rubber, and the electrostatic interaction between silica and graphene oxide The effect is a dynamic force that not only strengthens the cross-linked network structure of the graphene/natural rubber composite and greatly increases the cross-link density, but also enables the graphene filler to entangle a large amount of rubber during the dynamic movement of the rubber. The molecular chain enhances the interfacial interaction between graphene and the rubber matrix, thereby obtaining a graphene/natural rubber vulcanized rubber with improved mechanical, thermal conductivity and wear resistance properties.
本发明进一步提供了一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法，包括以下步骤：The invention further provides a preparation method of graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties, including the following steps:
(一)通过静电相互作用使二氧化硅负载在氧化石墨烯表面：将硅烷偶联剂KH550加入到水与乙醇的共混溶液中，分散均匀后得到硅烷偶联剂水解液；将二氧化硅加入到水与乙醇的共混溶液中，分散均匀后加入硅烷偶联剂水解液，一定温度下反应一段时间，抽滤、洗涤、干燥，得到氨基化改性二氧化硅粉末；(1) Load silica on the surface of graphene oxide through electrostatic interaction: Add silane coupling agent KH550 to the blended solution of water and ethanol, and disperse it evenly to obtain a silane coupling agent hydrolyzate; add silica Add to the blended solution of water and ethanol, disperse evenly, add the silane coupling agent hydrolyzate, react at a certain temperature for a period of time, filter, wash and dry to obtain amination modified silica powder;
将氨基化改性二氧化硅粉末加入到去离子水中并超声至分散均匀，然后滴加柠檬酸溶液，超声处理一定时间后，经多次离心、洗涤至分散液pH值为7，得到氨基质子化二氧化硅分散液，将其加入到氧化石墨烯水分散液中，超声处理一定时间，得到通过静电相互作用负载二氧化硅的氧化石墨烯的水分散液；Add aminated modified silica powder to deionized water and sonicate until dispersed evenly, then add citric acid solution dropwise, and after ultrasonic treatment for a certain period of time, centrifuge and wash multiple times until the pH value of the dispersion is 7 to obtain amino protons The silica dispersion is added to the graphene oxide aqueous dispersion, and ultrasonic treatment is performed for a certain period of time to obtain a graphene oxide aqueous dispersion loaded with silica through electrostatic interaction;
(二)水相协同聚沉工艺制备通过静电相互作用负载二氧化硅的氧化石墨烯/天然橡胶母胶：将去离子水加入到天然胶乳中，然后加入通过静电相互作用负载二氧化硅的氧化石墨烯的水分散液，均匀分散后得到混合乳液；加入絮凝剂，则负载二氧化硅的氧化石墨烯粒子和天然胶乳中的橡胶颗粒会以π-π作用力相互吸附，在水相中有序集聚并协同沉淀出来，得到生胶，水洗、除水、烘干，则得到通过静电相互作用负载二氧化硅的氧化石墨烯/天然橡胶母胶；(2) Preparation of graphene oxide/natural rubber masterbatch loaded with silica through electrostatic interaction by aqueous synergistic coagulation process: Add deionized water to natural rubber latex, and then add oxidized graphene oxide loaded with silica through electrostatic interaction. The aqueous dispersion of graphene is uniformly dispersed to obtain a mixed emulsion; when a flocculant is added, the silica-loaded graphene oxide particles and the rubber particles in the natural latex will adsorb each other through π-π forces, and there is The raw rubber is obtained by sequential aggregation and cooperative precipitation. After washing, removing water and drying, a graphene oxide/natural rubber masterbatch loaded with silica through electrostatic interaction is obtained;
(三)力学、导热和耐磨性能同时提升的石墨烯/天然橡胶硫化胶的制备：往步骤(二)制备的通过静电相互作用负载二氧化硅的改性氧化石墨烯/天然橡胶母胶中依次加入防老剂、抗氧化剂、活化剂及软化剂，密炼，分散均匀后得到混炼胶；往混炼胶中加入硫化促 进剂和硫化剂，然后进行开炼，混合均匀后，薄通至胶料无气泡，停放一定时间后将其放置于模具中，于一定温度和一定压力下硫化一定时间，得到力学、导热和耐磨性能同时提升的石墨烯/天然橡胶硫化胶。(3) Preparation of graphene/natural rubber vulcanized rubber with improved mechanical, thermal conductivity and wear resistance properties: Add the modified graphene oxide/natural rubber masterbatch loaded with silica through electrostatic interaction prepared in step (2) Add anti-aging agent, antioxidant, activator and softener in sequence, mix and disperse evenly to obtain a mixed rubber; add vulcanization accelerator to the mixed rubber Add additives and vulcanizing agents, and then start mixing. After mixing evenly, thin the rubber material until there are no bubbles. After leaving it for a certain period of time, place it in the mold and vulcanize it for a certain period of time at a certain temperature and pressure to obtain mechanical, thermal conductivity and Graphene/natural rubber vulcanized rubber with improved wear resistance.
作为本发明制备方法技术方案的进一步改进，步骤(一)中，水与乙醇按照1:1-3的体积比制备共混溶液；所述硅烷偶联剂KH550用量为二氧化硅质量的5-15％；反应温度为65-85℃，反应时间为4-8h；干燥温度为50-70℃。As a further improvement of the technical solution of the preparation method of the present invention, in step (1), water and ethanol are prepared in a volume ratio of 1:1-3; the dosage of the silane coupling agent KH550 is 5-5% of the mass of silica. 15%; reaction temperature is 65-85°C, reaction time is 4-8h; drying temperature is 50-70°C.
作为本发明制备方法技术方案的进一步改进，步骤(一)中，氨基化改性二氧化硅粉末在去离子水中的浓度为50-300mg/mL，柠檬酸溶液的浓度为1.5-4mol/L。As a further improvement of the technical solution of the preparation method of the present invention, in step (1), the concentration of amination-modified silica powder in deionized water is 50-300 mg/mL, and the concentration of citric acid solution is 1.5-4 mol/L.
作为本发明制备方法技术方案的进一步改进，步骤(一)中，氧化石墨烯水分散液的溶度是0.5-10mg/mL。As a further improvement of the technical solution of the preparation method of the present invention, in step (1), the solubility of the graphene oxide aqueous dispersion is 0.5-10 mg/mL.
作为本发明制备方法技术方案的进一步改进，步骤(一)中，氨基化改性二氧化硅粉末与柠檬酸的质量比为1-3:0.5-1；得到的通过静电相互作用负载二氧化硅的氧化石墨烯中氧化石墨烯与二氧化硅的质量比为1:10-60。As a further improvement of the technical solution of the preparation method of the present invention, in step (1), the mass ratio of amination-modified silica powder and citric acid is 1-3:0.5-1; the obtained silica is loaded by electrostatic interaction The mass ratio of graphene oxide to silicon dioxide in graphene oxide is 1:10-60.
作为本发明制备方法技术方案的进一步改进，步骤(一)中，超声分散的功率为50-300W。As a further improvement of the technical solution of the preparation method of the present invention, in step (1), the power of ultrasonic dispersion is 50-300W.
作为本发明制备方法技术方案的进一步改进，步骤(二)中，将去离子水加入到天然胶乳使天然胶乳乳液的浓度为10-40wt.％，所述絮凝剂的浓度为10wt.％，絮凝剂与天然橡胶的质量比为2-6:100。As a further improvement of the technical solution of the preparation method of the present invention, in step (2), deionized water is added to the natural rubber latex so that the concentration of the natural rubber latex emulsion is 10-40wt.%, the concentration of the flocculant is 10wt.%, and the flocculation The mass ratio of agent to natural rubber is 2-6:100.
作为本发明制备方法技术方案的进一步改进，步骤(三)中，所述防老剂、抗氧化剂、活化剂、软化剂、硫化促进剂、硫化剂的质量比为1:1:5:2:2:2。As a further improvement of the technical solution of the preparation method of the present invention, in step (3), the mass ratio of the antioxidant, antioxidant, activator, softener, vulcanization accelerator, and vulcanizing agent is 1:1:5:2:2 :2.
作为本发明制备方法技术方案的进一步改进，在石墨烯/天然橡胶硫化胶的制备过程中，所采用的天然橡胶为100质量份、通过静电相互作用负载二氧化硅的氧化石墨烯为0.5-30质量份、橡胶助剂为11-13质量份。As a further improvement of the technical solution of the preparation method of the present invention, in the preparation process of graphene/natural rubber vulcanized rubber, the natural rubber used is 100 parts by mass, and the graphene oxide loaded with silica through electrostatic interaction is 0.5-30 parts. The mass parts and rubber additives are 11-13 mass parts.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明采用高效、简洁、便于产业化生产的水相协同聚沉工艺制备石墨烯母胶，水相协同聚沉工艺可使制备的母胶保持均匀混合乳液中各组分的优异的分散效果，因此得到的母胶中石墨烯的分散良好；此外，进一步利用机械共混法使通过静电相互作用负载二氧化硅的氧化石墨烯更均匀的分散在天然橡胶硫化胶中，为最终得到力学、导热和耐磨性能同时提升的石墨烯/天然橡胶硫化胶奠定了工艺基础。 (1) The present invention adopts an efficient, simple, and easy-to-industrial production aqueous synergistic coagulation process to prepare graphene masterbatch. The aqueous synergistic coagulation process can enable the prepared masterbatch to maintain excellent properties of each component in the evenly mixed emulsion. The dispersion effect is good, so the graphene in the obtained masterbatch is well dispersed; in addition, the mechanical blending method is further used to make the graphene oxide loaded with silica through electrostatic interaction more uniformly dispersed in the natural rubber vulcanizate, which is the final result. The graphene/natural rubber vulcanized rubber with improved mechanical, thermal conductivity and wear resistance properties lays the foundation for the process.
(2)本发明使二氧化硅与氧化石墨烯之间形成静电相互作用，而二氧化硅与氧化石墨烯之间的静电相互作用是一种动态相互作用，不仅能够使石墨烯/天然橡胶复合材料的交联网络结构增强、交联密度大幅增加，而且在橡胶动态运动的过程中，能够使石墨烯填料缠结大量的橡胶分子链且使石墨烯与橡胶基体间的界面相互作用增强，为最终得到力学、导热和耐磨性能同时提升的石墨烯/天然橡胶硫化胶奠定了材料基础。(2) The present invention forms an electrostatic interaction between silica and graphene oxide, and the electrostatic interaction between silica and graphene oxide is a dynamic interaction, which not only enables graphene/natural rubber composite The cross-linked network structure of the material is enhanced and the cross-link density is greatly increased. During the dynamic movement of rubber, the graphene filler can entangle a large number of rubber molecular chains and enhance the interfacial interaction between graphene and the rubber matrix. Finally, the graphene/natural rubber vulcanized rubber with improved mechanical, thermal conductivity and wear resistance properties laid the material foundation.
(3)本发明的制备工艺简单且绿色环保，无任何苛刻要求，涉及到的均为常规设备，因此易于工业化生产，对于推进石墨烯在高性能橡胶领域中的应用具有重要意义。(3) The preparation process of the present invention is simple, green and environmentally friendly, without any harsh requirements, and involves conventional equipment. Therefore, it is easy for industrial production and is of great significance for promoting the application of graphene in the field of high-performance rubber.
附图说明Description of the drawings
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly explain the specific embodiments of the present invention or the technical solutions in the prior art, the accompanying drawings that need to be used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description The drawings illustrate some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting any creative effort.
图1为本发明实施例1和对比例2的二氧化硅及KH550改性二氧化硅的红外谱图。Figure 1 is the infrared spectrum of silica and KH550 modified silica in Example 1 and Comparative Example 2 of the present invention.
图2为本发明实施例1的通过静电相互作用负载二氧化硅的氧化石墨烯水分散液的电位图和氧化石墨烯的电位图。Figure 2 is a potential diagram of a graphene oxide aqueous dispersion that supports silica through electrostatic interaction and a potential diagram of graphene oxide in Example 1 of the present invention.
图3为GO和对比例2制备的SiO2-GO的(a)XPS全谱图、(b)GO的C 1s分峰拟合图、(c)SiO2-GO的C 1s分峰拟合图以及(d)SiO2-GO的N 1s分峰拟合图。Figure 3 shows (a) XPS full spectrum of GO and SiO 2 -GO prepared in Comparative Example 2, (b) C 1s peak fitting diagram of GO, (c) C 1s peak fitting of SiO 2 -GO Figure and (d) N 1s peak fitting diagram of SiO 2 -GO.
图4为利用不同的作用力负载纳米SiO2的GO的XRD谱图以及通过布拉格方程计算得到的GO的层间距d。Figure 4 shows the XRD spectrum of GO loaded with nano-SiO 2 using different forces and the interlayer spacing d of GO calculated by the Bragg equation.
图5为实施例1、对比例1和对比例2制备的天然橡胶复合材料的扭矩图。Figure 5 is a torque diagram of the natural rubber composite materials prepared in Example 1, Comparative Example 1 and Comparative Example 2.
图6是实施例1、对比例1和对比例2制备的天然橡胶硫化胶的(a)交联密度和(b)结合胶含量。Figure 6 shows (a) cross-linking density and (b) binder content of natural rubber vulcanized rubber prepared in Example 1, Comparative Example 1 and Comparative Example 2.
图7为大量含氧官能团使二氧化硅负载在氧化石墨烯表面的形态示意图。Figure 7 is a schematic diagram of the morphology of silica loaded on the surface of graphene oxide due to a large number of oxygen-containing functional groups.
具体实施方式Detailed ways
下面对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
本发明提供了一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法的具 体实施例，其中二氧化硅与氧化石墨烯之间静电相互作用形成负载纳米二氧化硅的氧化石墨烯，然后将负载纳米二氧化硅的氧化石墨烯加入到天然胶乳中，利用水相协同聚沉工艺制备得到石墨烯母胶，并进一步通过机械共混法和硫化工艺得到石墨烯/天然橡胶。The invention provides a method for preparing graphene/natural rubber with improved mechanical, thermal conductivity and wear resistance properties. In a specific embodiment, the electrostatic interaction between silica and graphene oxide forms graphene oxide loaded with nano-silica, and then the graphene oxide loaded with nano-silica is added to the natural latex, and the water phase is used to synergistically polymerize The graphene masterbatch is prepared by the precipitation process, and graphene/natural rubber is further obtained through mechanical blending and vulcanization processes.
本发明进一步提供了一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法，包括以下步骤：The invention further provides a preparation method of graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties, including the following steps:
(一)通过静电相互作用使二氧化硅负载在氧化石墨烯表面：将硅烷偶联剂KH550加入到水与乙醇的共混溶液中，分散均匀后得到硅烷偶联剂水解液；将二氧化硅加入到水与乙醇的共混溶液中，分散均匀后加入硅烷偶联剂水解液，一定温度下反应一段时间，抽滤、洗涤、干燥，得到氨基化改性二氧化硅粉末；(1) Load silica on the surface of graphene oxide through electrostatic interaction: Add silane coupling agent KH550 to the blended solution of water and ethanol, and disperse it evenly to obtain a silane coupling agent hydrolyzate; add silica Add to the blended solution of water and ethanol, disperse evenly, add the silane coupling agent hydrolyzate, react at a certain temperature for a period of time, filter, wash and dry to obtain amination modified silica powder;
将氨基化改性二氧化硅粉末加入到去离子水中并超声至分散均匀，然后滴加柠檬酸溶液，超声处理一定时间后，经多次离心、洗涤至分散液pH值为7，得到氨基质子化二氧化硅分散液，将其加入到氧化石墨烯水分散液中，超声处理一定时间，得到通过静电相互作用负载二氧化硅的氧化石墨烯的水分散液；Add aminated modified silica powder to deionized water and sonicate until dispersed evenly, then add citric acid solution dropwise, and after ultrasonic treatment for a certain period of time, centrifuge and wash multiple times until the pH value of the dispersion is 7 to obtain amino protons The silica dispersion is added to the graphene oxide aqueous dispersion, and ultrasonic treatment is performed for a certain period of time to obtain a graphene oxide aqueous dispersion loaded with silica through electrostatic interaction;
(二)水相协同聚沉工艺制备通过静电相互作用负载二氧化硅的氧化石墨烯/天然橡胶母胶：将去离子水加入到天然胶乳中，然后加入通过静电相互作用负载二氧化硅的氧化石墨烯的水分散液，均匀分散后得到混合乳液；加入絮凝剂，则负载二氧化硅的氧化石墨烯粒子和天然胶乳中的橡胶颗粒会以π-π作用力相互吸附，在水相中有序集聚并协同沉淀出来，得到生胶，水洗、除水、烘干，则得到通过静电相互作用负载二氧化硅的氧化石墨烯/天然橡胶母胶；(2) Preparation of graphene oxide/natural rubber masterbatch loaded with silica through electrostatic interaction by aqueous synergistic coagulation process: Add deionized water to natural rubber latex, and then add oxidized graphene oxide loaded with silica through electrostatic interaction. The aqueous dispersion of graphene is uniformly dispersed to obtain a mixed emulsion; when a flocculant is added, the silica-loaded graphene oxide particles and the rubber particles in the natural latex will adsorb each other through π-π forces, and there is The raw rubber is obtained by sequential aggregation and cooperative precipitation. After washing, removing water and drying, a graphene oxide/natural rubber masterbatch loaded with silica through electrostatic interaction is obtained;
(三)力学、导热和耐磨性能同时提升的石墨烯/天然橡胶硫化胶的制备：往步骤(二)制备的通过静电相互作用负载二氧化硅的改性氧化石墨烯/天然橡胶母胶中依次加入防老剂、抗氧化剂、活化剂及软化剂，密炼，分散均匀后得到混炼胶；往混炼胶中加入硫化促进剂和硫化剂，然后进行开炼，混合均匀后，薄通至胶料无气泡，停放一定时间后将其放置于模具中，于一定温度和一定压力下硫化一定时间，得到力学、导热和耐磨性能同时提升的石墨烯/天然橡胶硫化胶。(3) Preparation of graphene/natural rubber vulcanized rubber with improved mechanical, thermal conductivity and wear resistance properties: Add the modified graphene oxide/natural rubber masterbatch loaded with silica through electrostatic interaction prepared in step (2) Add anti-aging agent, antioxidant, activator and softener in sequence, mix and disperse evenly to obtain a rubber mixture; add vulcanization accelerator and vulcanizing agent to the rubber mixture, and then start kneading. After mixing evenly, pass it to a thin layer. The rubber has no bubbles. After it has been parked for a certain period of time, it is placed in the mold and vulcanized for a certain period of time at a certain temperature and pressure to obtain graphene/natural rubber vulcanized rubber with improved mechanical, thermal conductivity and wear resistance properties.
本发明还提供了上述制备方法的相关制备机理：The present invention also provides the relevant preparation mechanism of the above preparation method:
(1)在水解过程中，KH550硅烷偶联剂所含有的乙氧基会水解成羟基，中间产物为硅醇，硅醇中的羟基与二氧化硅表面的羟基发生脱水缩合反应，从而使二氧化硅表面接枝其它官能团，随后在超声作用的辅助下，在酸性条件下将二氧化硅表面接枝的氨基质子化，相关反应机理如下所示。
(1) During the hydrolysis process, the ethoxy groups contained in the KH550 silane coupling agent will be hydrolyzed into hydroxyl groups, and the intermediate product is silanol. The hydroxyl groups in the silanol and the hydroxyl groups on the surface of the silica undergo a dehydration condensation reaction, thereby causing the silanol to form. The surface of silicon oxide is grafted with other functional groups, and then with the assistance of ultrasound, the amino groups grafted on the surface of silicon dioxide are protonated under acidic conditions. The relevant reaction mechanism is as follows.
(2)改性二氧化硅表面的氨正离子与氧化石墨烯表面的大量含氧官能团之间的静电相互作用使二氧化硅负载在氧化石墨烯表面，具体参见图7。其中图7(a)为GO片层和SiO2-NH3+的形态示意图，图7(b)为二氧化硅负载在氧化石墨烯表面的形态示意图。(2) The electrostatic interaction between the ammonia cations on the surface of modified silica and the large number of oxygen-containing functional groups on the surface of graphene oxide causes silica to be loaded on the surface of graphene oxide. See Figure 7 for details. Figure 7(a) is a schematic diagram of the morphology of GO sheets and SiO 2 -NH 3+ , and Figure 7(b) is a schematic diagram of the morphology of silicon dioxide supported on the surface of graphene oxide.
具体的，步骤(一)中，水与乙醇按照1:1-3的体积比制备共混溶液；所述硅烷偶联剂KH550用量为二氧化硅质量的5-15％；反应温度为65-85℃，反应时间为4-8h；干燥温度为50-70℃。优选的，所述水与乙醇按照1:3的体积比制备共混溶液；所述硅烷偶联剂KH550用量为二氧化硅质量的10-12％；反应温度为70-80℃，反应时间为5-7h；干燥温度为70℃。Specifically, in step (1), water and ethanol are prepared in a volume ratio of 1:1-3; the dosage of the silane coupling agent KH550 is 5-15% of the mass of silica; the reaction temperature is 65- 85℃, reaction time is 4-8h; drying temperature is 50-70℃. Preferably, the water and ethanol prepare a blend solution according to the volume ratio of 1:3; the dosage of the silane coupling agent KH550 is 10-12% of the mass of silica; the reaction temperature is 70-80°C, and the reaction time is 5-7h; drying temperature is 70℃.
进一步的，步骤(一)中，氨基化改性二氧化硅粉末在去离子水中的浓度为50-300mg/mL，柠檬酸溶液的浓度为1.5-4mol/L。Further, in step (1), the concentration of amination-modified silica powder in deionized water is 50-300 mg/mL, and the concentration of citric acid solution is 1.5-4 mol/L.
更进一步的，步骤(一)中，氧化石墨烯水分散液的溶度是0.5-10mg/mL。Furthermore, in step (1), the solubility of the graphene oxide aqueous dispersion is 0.5-10 mg/mL.
在本发明中，步骤(一)中，氨基化改性二氧化硅粉末与柠檬酸的质量比为1-3:0.5-1；得到的通过静电相互作用负载二氧化硅的氧化石墨烯中氧化石墨烯与二氧化硅的质量比为1:10-60。In the present invention, in step (1), the mass ratio of aminated modified silica powder and citric acid is 1-3:0.5-1; the obtained graphene oxide loading silica through electrostatic interaction is oxidized The mass ratio of graphene to silica is 1:10-60.
优选的，步骤(一)中，超声分散的功率为50-300W。Preferably, in step (1), the power of ultrasonic dispersion is 50-300W.
进一步的，步骤(二)中，将去离子水加入到天然胶乳使天然胶乳乳液的浓度为10-40wt.％，所述絮凝剂的浓度为10wt.％，絮凝剂与天然橡胶的质量比为2-6:100。Further, in step (2), deionized water is added to the natural rubber latex so that the concentration of the natural rubber latex emulsion is 10-40wt.%, the concentration of the flocculant is 10wt.%, and the mass ratio of the flocculant to the natural rubber is 2-6:100.
具体实施时，步骤(二)中，所述絮凝剂为氯化钙溶液、氯化钠溶液、氯化钾溶液、硫酸钠溶液、盐酸溶液和甲酸溶液中的至少一种。In specific implementation, in step (2), the flocculant is at least one of calcium chloride solution, sodium chloride solution, potassium chloride solution, sodium sulfate solution, hydrochloric acid solution and formic acid solution.
更进一步的，步骤(三)中，所述防老剂、抗氧化剂、活化剂、软化剂、硫化促进剂、硫化剂的质量比为1:1:5:2:2:2。Furthermore, in step (3), the mass ratio of the antioxidant, antioxidant, activator, softener, vulcanization accelerator, and vulcanizing agent is 1:1:5:2:2:2.
在本发明提供的一个实施例中，在石墨烯/天然橡胶硫化胶的制备过程中，所采用的天然橡胶为100质量份、通过静电相互作用负载二氧化硅的氧化石墨烯为0.5-30质量份、橡胶助剂为11-13质量份。In one embodiment provided by the present invention, in the preparation process of graphene/natural rubber vulcanizate, the natural rubber used is 100 parts by mass, and the graphene oxide loaded with silica through electrostatic interaction is 0.5-30 parts by mass. parts and rubber additives are 11-13 parts by mass.
在本发明提供的另外一个实施例中，步骤(三)中，所述硫化促进剂为N-叔丁基-2-苯并噻唑次磺酰胺、N-环己基-2-苯并噻唑次磺酰胺或N-(氧化二亚乙基)-2-苯并噻唑次磺酰胺； 硫化剂为硫磺或一氯化硫；防老剂为2,6-二叔丁基-4-甲基苯酚、2,2,4-三甲基-1,2-二氢化喹啉聚合体或2-硫醇基苯骈咪唑；抗氧化剂为N-异丙基-N’-苯基对苯二胺、对苯基苯胺或硫化二丙酸二月桂酯；活化剂为葡萄酸锌、氧化锌或氧化镁；软化剂为硬脂酸、钛酸二丁酯或己二酸二辛脂。In another embodiment provided by the present invention, in step (3), the vulcanization accelerator is N-tert-butyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide Amide or N-(diethylene oxide)-2-benzothiazole sulfenamide; The vulcanizing agent is sulfur or sulfur monochloride; the antioxidant is 2,6-di-tert-butyl-4-methylphenol, 2,2,4-trimethyl-1,2-dihydroquinoline polymer or 2 -Thiobenzoimidazole; the antioxidant is N-isopropyl-N'-phenyl-p-phenylenediamine, p-phenylaniline or dilauryl sulfide dipropionate; the activator is zinc glucate, zinc oxide or Magnesium oxide; softener is stearic acid, dibutyl titanate or dioctyl adipate.
在本发明提供的另外一个实施例中，步骤(三)中，密炼机的混炼温度105-120℃，混炼时间为3-5min；开炼温度50-70℃，开炼时间为8-12min；混炼胶的停放时间为18-36h；硫化温度135-170℃，硫化压力10-30MPa，硫化时间10-25min。In another embodiment provided by the present invention, in step (3), the mixing temperature of the internal mixer is 105-120°C, the mixing time is 3-5 minutes; the mixing temperature is 50-70°C, and the mixing time is 8 -12min; the storage time of the mixed rubber is 18-36h; the vulcanization temperature is 135-170℃, the vulcanization pressure is 10-30MPa, and the vulcanization time is 10-25min.
下面通过具体实施例来对本发明的技术方案进行详细的说明。The technical solution of the present invention will be described in detail below through specific embodiments.
实施例1～4Examples 1 to 4
一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法，包括以下步骤：A preparation method of graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties, including the following steps:
(1)称取11g硅烷偶联剂KH550，加入到33g去离子水与66g乙醇的共混溶液中，超声搅拌15min后继续机械搅拌45min，以使KH550充分水解。称取100g二氧化硅，加入到乙醇和蒸馏水比例为3:1的100ml溶液中，100w功率超声分散30min后，加入配制的硅烷偶联剂水解液，75℃反应6h，抽滤、洗涤，70℃干燥至恒重，得到氨基化二氧化硅粉末，表示为m-SiO2。(1) Weigh 11g of silane coupling agent KH550, add it to a blended solution of 33g of deionized water and 66g of ethanol, stir ultrasonically for 15 minutes and then continue mechanical stirring for 45 minutes to fully hydrolyze KH550. Weigh 100g of silica and add it to 100ml of a solution with a ratio of ethanol to distilled water of 3:1. After ultrasonic dispersion at 100w for 30 minutes, add the prepared silane coupling agent hydrolyzate, react at 75°C for 6 hours, filter and wash with 70 °C to constant weight to obtain aminated silica powder, expressed as m-SiO 2 .
将m-SiO2粉末加入到去离子水中，超声分散20min，然后按照氨基化改性二氧化硅粉末与柠檬酸质量比5:4.41加入配制的浓度2.3mol/L的柠檬酸溶液，超声1h后，离心、洗涤至中性，得到氨基质子化二氧化硅溶液，表示为SiO2-NH3 +。Add m-SiO 2 powder to deionized water, disperse with ultrasonic for 20 minutes, then add the prepared citric acid solution with a concentration of 2.3 mol/L according to the mass ratio of aminated modified silica powder to citric acid 5:4.41, and after ultrasonic for 1 hour , centrifuge and wash until neutral to obtain an amino protonated silica solution, expressed as SiO 2 -NH 3 + .
(2)配制浓度为0.5mg/mL的氧化石墨烯水分散液。(2) Prepare a graphene oxide aqueous dispersion with a concentration of 0.5 mg/mL.
(3)将步骤(1)制备的不同质量的氨基质子化二氧化硅分散液加入到步骤(2)得到的250mL氧化石墨烯分散液中，室温下超声分散15min，得到通过静电相互作用负载二氧化硅的氧化石墨烯水分散液，表示为SiO2-NH3 +/GO，具体原料二氧化硅和氧化石墨烯的质量见表1。(3) Add the amino protonated silica dispersions of different masses prepared in step (1) to the 250 mL graphene oxide dispersion obtained in step (2), and disperse it ultrasonically for 15 minutes at room temperature to obtain the dielectric loaded by electrostatic interaction. The aqueous dispersion of graphene oxide of silicon oxide is expressed as SiO 2 -NH 3 + /GO. The specific mass of the raw materials silica and graphene oxide is shown in Table 1.
(4)将一定量的去离子水加入到天然胶乳中(167g，固含量60wt.％)，搅拌至均匀，得到浓度为20wt.％的天然胶乳乳液，然后分别加入不同质量的步骤(3)制备的通过静电相互作用负载二氧化硅的氧化石墨烯(SiO2-NH3 +/GO)分散液，充分搅拌混合后，得到分散均匀的混合乳液；加入絮凝剂10wt.％的CaCl2溶液25g，因此，改性氧化石墨烯粒子和橡胶颗粒在水相中有序集聚并协同沉淀出来；将得到的生胶水洗、除水、在65℃的烘箱中烘干至恒重，则得到通过静电相互作用负载二氧化硅的氧化石墨烯/天然橡胶母胶。(4) Add a certain amount of deionized water to the natural rubber latex (167g, solid content 60wt.%), stir until uniform, obtain a natural rubber latex emulsion with a concentration of 20wt.%, and then add steps (3) of different masses. The prepared graphene oxide (SiO 2 -NH 3 + /GO) dispersion loaded with silica through electrostatic interaction was thoroughly stirred and mixed to obtain a uniformly dispersed mixed emulsion; 25g of 10wt.% CaCl 2 solution of flocculant was added , therefore, the modified graphene oxide particles and rubber particles gather in an orderly manner in the water phase and precipitate cooperatively; the obtained raw rubber is washed with water, removed from the water, and dried in an oven at 65°C to a constant weight, and then the result obtained by electrostatic Interaction-loaded silica-loaded graphene oxide/natural rubber masterbatch.
(5)将步骤(4)得到的通过静电相互作用负载二氧化硅的氧化石墨烯/天然橡胶母胶 置于密炼机中，在110℃和40rpm条件下混炼，期间分三次加入1g抗氧化剂4010NA、1g防老剂RD，5g活化剂ZnO、2g软化剂SA，每次混炼4min，排出胶料。胶料冷却至室温后，将其转移至开炼机上，60℃开炼，分散均匀后加入2g硫化促进剂NOBS、2g硫磺，混合均匀后，薄通至胶料无气泡。停胶24h后，混炼胶经硫化机在150℃和15MPa下硫化一定时间(tC90)，得到多性能同时优化天然橡胶硫化胶，其中tC90由橡胶加工分析仪(RPA)测得。(5) Use the graphene oxide/natural rubber masterbatch obtained in step (4) to load silica through electrostatic interaction. Place it in an internal mixer and mix at 110°C and 40 rpm. During this period, add 1g of antioxidant 4010NA, 1g of antioxidant RD, 5g of activator ZnO, and 2g of softener SA in three batches. Mix for 4 minutes each time and discharge the rubber material. . After the rubber material is cooled to room temperature, transfer it to the open mill and start mixing at 60°C. After evenly dispersed, add 2g of vulcanization accelerator NOBS and 2g of sulfur. After mixing evenly, mix until the rubber material has no bubbles. After 24 hours of rubber stoppage, the mixed rubber was vulcanized for a certain period of time (t C90 ) at 150°C and 15 MPa in a vulcanizer to obtain a multi-performance simultaneously optimized natural rubber vulcanized rubber, in which t C90 was measured by a rubber processing analyzer (RPA).
对比例1：(SiO2通过氢键负载在GO表面，表示为SiO2/GO)Comparative Example 1: (SiO 2 is loaded on the surface of GO through hydrogen bonds, expressed as SiO 2 /GO)
称取适量的SiO2，经超声分散在去离子水中得到均匀分散液；配制浓度为0.5mg/mL的氧化石墨烯水分散液，然后将已超声分散均匀的SiO2溶液分多次加入，混合均匀后，得到通过氢键负载SiO2的GO的水分散液。具体二氧化硅和氧化石墨烯的质量见表1。Weigh an appropriate amount of SiO 2 and disperse it in deionized water via ultrasonic to obtain a uniform dispersion; prepare a graphene oxide aqueous dispersion with a concentration of 0.5 mg/mL, then add the SiO 2 solution that has been uniformly dispersed by ultrasonic in several batches, and mix After homogenization, an aqueous dispersion of GO supporting SiO2 through hydrogen bonds was obtained. The specific masses of silica and graphene oxide are shown in Table 1.
随后氧化石墨烯/天然橡胶母胶以及硫化胶制备工艺与实施例1-4的步骤(4)和(5)完全相同，唯一不同之处是将实施例1-4中的通过静电相互作用负载二氧化硅的氧化石墨烯(SiO2-NH3 +/GO)分散液更换为通过氢键负载SiO2的GO(SiO2/GO)分散液。The subsequent graphene oxide/natural rubber masterbatch and vulcanized rubber preparation processes are exactly the same as steps (4) and (5) in Example 1-4. The only difference is that the graphene oxide/natural rubber masterbatch and vulcanized rubber preparation process in Example 1-4 are loaded by electrostatic interaction. The graphene oxide (SiO 2 -NH 3 + /GO) dispersion of silicon dioxide is replaced with a GO (SiO 2 /GO) dispersion that supports SiO 2 through hydrogen bonds.
对比例2：(SiO2通过化学结合力负载在GO表面，表示为SiO2-GO)Comparative Example 2: (SiO 2 is loaded on the surface of GO through chemical binding force, expressed as SiO 2 -GO)
(1)按照与实施例1-4完全相同的工艺制备氨基质子化二氧化硅溶液，然后将其超声分散在去离子水中。(1) Prepare an amino protonated silica solution according to the same process as Example 1-4, and then disperse it in deionized water by ultrasonic.
(2)配制浓度为0.5mg/mL的氧化石墨烯水分散液。(2) Prepare a graphene oxide aqueous dispersion with a concentration of 0.5 mg/mL.
(3)将步骤(1)制备的质子化二氧化硅分散液加入到步骤(2)得到的250mL氧化石墨烯分散液中，室温下超声分散15min，然后，滴加一定浓度的N-羟基琥珀酰亚胺溶液，磁力搅拌30min后，缓慢滴加1-乙基-3-(3-二甲基氨基丙基)碳酰二亚胺溶液，在冰浴条件下磁力搅拌24h，制得通过化学结合力负载SiO2的GO水分散液。具体二氧化硅和氧化石墨烯的质量见表1。(3) Add the protonated silica dispersion prepared in step (1) to the 250 mL graphene oxide dispersion obtained in step (2), ultrasonically disperse it at room temperature for 15 minutes, and then add a certain concentration of N-hydroxysmber dropwise Imide solution, stir magnetically for 30 minutes, slowly add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide solution dropwise, stir magnetically under ice bath conditions for 24h, and prepare by chemical Binding force-loaded SiO 2 aqueous dispersion of GO. The specific masses of silica and graphene oxide are shown in Table 1.
随后氧化石墨烯/天然橡胶母胶以及硫化胶制备工艺与实施例1-4的步骤(4)和(5)完全相同，唯一不同之处是将实施例1-4中的通过静电相互作用负载二氧化硅的氧化石墨烯(SiO2-NH3 +/GO)分散液更换为通过化学结合力负载SiO2的GO(SiO2-GO)分散液。The subsequent graphene oxide/natural rubber masterbatch and vulcanized rubber preparation processes are exactly the same as steps (4) and (5) in Example 1-4. The only difference is that the graphene oxide/natural rubber masterbatch and vulcanized rubber preparation process in Example 1-4 are loaded by electrostatic interaction. The graphene oxide (SiO 2 -NH 3 + /GO) dispersion of silicon dioxide is replaced with a GO (SiO 2 -GO) dispersion that supports SiO 2 through chemical binding force.
对比例3：Comparative example 3:
与实施例1～4的区别在于：不加纳米二氧化硅，为氧化石墨烯/天然橡胶复合材料，即不包括实施例1～4制备工艺中的步骤(1)、(2)和(3)，与实施例1-4的步骤(4)和(5)完全相同，即将实施例1-4中的通过静电相互作用负载二氧化硅的氧化石墨烯(SiO2-NH3 +/GO)分散液更换为GO分散液。 The difference from Examples 1 to 4 is that no nano-silica is added and it is a graphene oxide/natural rubber composite material, that is, steps (1), (2) and (3) in the preparation process of Examples 1 to 4 are not included. ), which are exactly the same as steps (4) and (5) in Example 1-4, that is, graphene oxide (SiO 2 -NH 3 + /GO) loaded with silica through electrostatic interaction in Example 1-4 The dispersion liquid was replaced with GO dispersion liquid.
实施例和对比例的配方见表1，性能测试结果见表2。The formulas of the examples and comparative examples are shown in Table 1, and the performance test results are shown in Table 2.
表1实施例1～4与对比例1～3的配方表
Table 1 Formula tables of Examples 1 to 4 and Comparative Examples 1 to 3
其中性能测试标准如下所示：The performance test standards are as follows:
(1)傅里叶变换红外光谱分析(1) Fourier transform infrared spectroscopy analysis
采用美国热电公司的IS50傅里叶变换红外光谱分析仪对SiO2和m-SiO2进行官能团分析，测试范围为500-4000cm-1，测试方法将试样与KBr粉末按1:100研磨混合均匀，压成薄片。The IS50 Fourier transform infrared spectrometer of American Thermoelectric Company was used to conduct functional group analysis on SiO 2 and m-SiO 2. The test range was 500-4000cm -1 . The test method was to grind the sample and KBr powder at a ratio of 1:100 and mix them evenly. , pressed into thin slices.
图1中，3410cm-1归因于SiO2表面羟基-OH拉伸振动，SiO2特有的Si-O-Si的对称伸缩振动峰在795cm-1处以及在1066cm-1处对应Si-O-Si的反对称伸缩振动峰。从m-SiO2红外谱图中可以清晰地看到，在1633cm-1处为-NH2中N-H的面内变形振动峰，以及在2930cm-1处特有的C-H的伸缩振动峰，表明硅烷偶联剂KH550成功改性SiO2。In Figure 1, 3410cm -1 is attributed to the hydroxyl-OH stretching vibration on the SiO 2 surface. The symmetric stretching vibration peaks of Si-O-Si unique to SiO 2 are at 795cm -1 and 1066cm -1 corresponding to Si-O- The antisymmetric stretching vibration peak of Si. It can be clearly seen from the infrared spectrum of m-SiO 2 that the in-plane deformation vibration peak of NH in -NH 2 at 1633cm -1 and the unique stretching vibration peak of CH at 2930cm -1 indicate that the silane coupling Joint agent KH550 successfully modified SiO 2 .
(2)X射线衍射分析(2)X-ray diffraction analysis
采用丹东方圆DX-2700B型X射线衍射分析仪，通过Cu-Kα辐射的X射线对GO、SiO2/GO、SiO2-NH3 +/GO和SiO2-GO的晶体结构进行测试分析，测试的扫描角度是5-80°，采样时间是0.2s，步进角度为0.03°。然后，通过布拉格方程，如下式所示，计算得到GO的层间距。
λ＝2d sinθThe Dandongfang Yuan DX-2700B X-ray diffraction analyzer was used to test and analyze the crystal structures of GO, SiO 2 /GO, SiO 2 -NH 3 + /GO and SiO 2 -GO through X-rays radiated by Cu-Kα. The scanning angle is 5-80°, the sampling time is 0.2s, and the step angle is 0.03°. Then, the interlayer spacing of GO is calculated through the Bragg equation, as shown in the following formula.
λ=2d sinθ
由图4可知，引入纳米SiO2以后，GO的层间距均明显增大，直接证明在超声作用下，纳米SiO2成功插层到GO的片层间。相较于对比例1的纳米SiO2与GO之间的氢键相互作用，本发明的纳米SiO2与GO之间的静电相互作用以及对比例2的纳米SiO2与GO之间的化学键作用使得GO的层间距更大。与此同时，也可以明显看出，对比例2的层间存 在化学键作用的GO的层间距远小于本发明的纳米SiO2与GO之间的静电相互作用的GO的层间距，表明本发明的GO与SiO2之间良好的化学结合，也进一步验证了GO与SiO2之间的静电相互作用力是一种可逆相互作用力。As can be seen from Figure 4, after the introduction of nano-SiO 2 , the interlayer spacing of GO increased significantly, which directly proves that nano-SiO 2 was successfully intercalated into the layers of GO under the action of ultrasound. Compared with the hydrogen bond interaction between nano-SiO 2 and GO in Comparative Example 1, the electrostatic interaction between nano-SiO 2 and GO of the present invention and the chemical bond interaction between nano-SiO 2 and GO in Comparative Example 2 make The layer spacing of GO is larger. At the same time, it can also be clearly seen that the interlayer existence in Comparative Example 2 The interlayer spacing of GO due to chemical bonding is much smaller than the interlayer spacing of GO due to the electrostatic interaction between nano-SiO 2 and GO of the present invention, indicating a good chemical combination between the GO of the present invention and SiO 2 and further verifying that GO The electrostatic interaction force with SiO2 is a reversible interaction force.
(3)Zeta电位分析(3)Zeta potential analysis
采用欧美克公司NS-90Z型Zeta电位分析仪测试SiO2-NH3 +和GO稳定分散液的电位。The potential of the SiO 2 -NH 3 + and GO stabilized dispersion was tested using the NS-90Z Zeta potential analyzer of Euro-American Company.
图2清晰地显示了GO和SiO2-NH3+的Zeta电位图。由图可以明确，改性后的SiO2在经过柠檬酸处理后，其表面接枝的氨基通过酸进行质子化，使得稀释后的二氧化硅分散液带上正电，经过Zeta电位分析仪测得，SiO2分散液的电位为+43mv。然而，经Zeta电位分析仪测得，氧化石墨烯分散液的电位为-40mv。这就能够清晰地表明，改性SiO2中的氨基被酸成功质子化，并且经过酸质子化改性的SiO2电位分散液与稀释后的氧化石墨烯分散液内分别存在正负电荷，且他们有明显静电吸附效果。Figure 2 clearly shows the zeta potential diagrams of GO and SiO 2 -NH 3+ . It is clear from the figure that after the modified SiO 2 is treated with citric acid, the amino groups grafted on the surface are protonated by the acid, making the diluted silica dispersion positively charged, and measured by a Zeta potential analyzer. Obtained, the potential of SiO 2 dispersion is +43mv. However, the potential of the graphene oxide dispersion was -40mv as measured by a Zeta potential analyzer. This can clearly show that the amino groups in modified SiO 2 are successfully protonated by acid, and there are positive and negative charges respectively in the SiO 2 potential dispersion modified by acid protonation and the diluted graphene oxide dispersion, and They have obvious electrostatic adsorption effect.
(4)X射线光电子能谱分析(4)X-ray photoelectron spectroscopy analysis
采用美国赛默飞公司的NEXSA型X射线光电子能谱分析仪对GO和SiO2-GO表面元素及其化学组成成分的变化进行测试分析。测试扫描是CAE模式，全谱扫描的通能为160eV，窄谱的扫描的通能为40eV。The NEXSA X-ray photoelectron spectrometer analyzer from Thermo Fisher Company in the United States was used to test and analyze changes in surface elements and chemical compositions of GO and SiO 2 -GO. The test scan is in CAE mode, the pass of full spectrum scan is 160eV, and the pass of narrow spectrum scan is 40eV.
图3(a)为GO和对比例2制备的SiO2-GO的XPS全谱图。从图中可以明确看出，SiO2-GO的XPS全谱中有Si特征的Si 2s和Si 2p峰，以及特征的N 1s峰。图3(b)中，284.8eV和286.8eV分别对应C＝C和C-O，C＝O，O-C＝O分别与287.8eV和288.5eV处相匹配。图3(c)中，285.8eV处有新的C-N峰出现，表明氧化石墨烯表面的含氧官能团和SiO2表面的氨基发生了酰胺化反应，同时也证明氧化石墨烯与SiO2之间的化学结合。图3(d)中，399.3eV处出现＝N-的峰，400.3eV对应-N-H的峰，401.7eV处对应-NH2的峰。通过对N谱的分峰拟合，直接证明SiO2-GO中GO与改性SiO2间的化学结合。Figure 3(a) shows the full XPS spectrum of GO and SiO 2 -GO prepared in Comparative Example 2. It can be clearly seen from the figure that the XPS full spectrum of SiO 2 -GO has the characteristic Si 2s and Si 2p peaks of Si, as well as the characteristic N 1s peak. In Figure 3(b), 284.8eV and 286.8eV correspond to C=C and CO respectively, and C=O and OC=O match 287.8eV and 288.5eV respectively. In Figure 3(c), a new CN peak appears at 285.8eV, indicating that the amidation reaction between the oxygen-containing functional groups on the surface of graphene oxide and the amino group on the surface of SiO 2 has occurred. It also proves that the interaction between graphene oxide and SiO 2 Chemical bonding. In Figure 3(d), a peak of =N- appears at 399.3eV, a peak corresponding to -NH appears at 400.3eV, and a peak corresponding to -NH 2 appears at 401.7eV. By fitting the peaks of the N spectrum, the chemical combination between GO and modified SiO 2 in SiO 2 -GO is directly proved.
(5)橡胶加工分析(5)Rubber processing analysis
采用台湾高铁公司的RPA-8000橡胶加工分析仪对混炼胶的硫化特性进行分析。测试条件是称取混炼胶3-5g，两侧用玻璃纸覆盖，放置在温度为150℃的转子上，测得最佳的硫化时间和相应的扭矩值。The RPA-8000 rubber processing analyzer of Taiwan High Speed Rail Corporation was used to analyze the vulcanization characteristics of the rubber compound. The test conditions are to weigh 3-5g of the mixed rubber, cover both sides with cellophane paper, place it on a rotor with a temperature of 150°C, and measure the optimal vulcanization time and corresponding torque value.
从图5(a)中可以明显看出，实施例1制备的石墨烯/天然橡胶的扭矩差值最大，表明该复合材料中石墨烯与天然橡胶基体间形成的交联网络结构最多，这主要归因于静电力为一种可逆力，使得整个复合系统的网络结构增强，从而在宏观上表现为GO/SiO2-NH3 +/NR的扭矩差值最大。图5(b)是橡胶复合材料的应变扫描图，其表明氧化石墨烯层间存在静电作 用时，即实施例1制备的石墨烯/天然橡胶复合材料中填料在橡胶基体中的分散效果最好。It can be clearly seen from Figure 5(a) that the graphene/natural rubber prepared in Example 1 has the largest torque difference, indicating that the composite material has the largest cross-linked network structure between graphene and the natural rubber matrix. This is mainly Since the electrostatic force is a reversible force, the network structure of the entire composite system is enhanced, thus macroscopically manifesting as the largest torque difference of GO/SiO 2 -NH 3 + /NR. Figure 5(b) is a strain scan of the rubber composite material, which shows that there are electrostatic interactions between graphene oxide layers. When used, that is, the graphene/natural rubber composite material prepared in Example 1 has the best dispersion effect of the filler in the rubber matrix.
(6)交联密度及结合胶含量测试(6) Cross-linking density and binding glue content testing
称取质量为1g的最终得到的天然橡胶复合材料，称重并记为m0，浸泡在适量的甲苯溶剂中，每隔24h更换一次甲苯溶剂，待72h后，将溶胀物取出，放置在滤纸上。待表面甲苯去除干净后，称其重量，记为m1。然后，将其放置在50℃的鼓风干燥箱中干燥至恒重，称重并记为m2。橡胶复合材料的交联密度通过下列公式求出：
Weigh the final natural rubber composite material with a mass of 1g, weigh it and record it as m 0 , soak it in an appropriate amount of toluene solvent, replace the toluene solvent every 24 hours, and after 72 hours, take out the swollen material and place it on filter paper superior. After the toluene on the surface is completely removed, weigh it and record it as m 1 . Then, place it in a forced air drying oven at 50°C to dry to constant weight, weigh it and record it as m 2 . The cross-link density of rubber composites is determined by the following formula:
式中：Vr是平衡溶胀物中橡胶的体积分率，φ是试样中橡胶的质量分数，α是在溶胀过程中试样的质量损失率，ρr是橡胶复合材料的密度，ρs是溶剂甲苯的密度。In the formula: V r is the volume fraction of rubber in the equilibrium swelling material, φ is the mass fraction of rubber in the sample, α is the mass loss rate of the sample during the swelling process, ρ r is the density of the rubber composite material, ρ s is the density of the solvent toluene.
根据Flory-Rehner公式计算橡胶复合材料的交联密度：
Calculate the cross-link density of rubber composites according to the Flory-Rehner formula:
式中：Ve是橡胶的交联密度，Vs是溶剂甲苯的摩尔体积，χ是橡胶与甲苯间的溶剂作用参数。In the formula: V e is the cross-linking density of rubber, V s is the molar volume of solvent toluene, and χ is the solvent interaction parameter between rubber and toluene.
采用差式扫描量热仪对橡胶复合材料的结合胶含量进行测试和分析。所有试验条件都在-80℃-25℃的温度下进行，加热速率为5℃/min。橡胶复合材料的结合胶含量根据下列公式求出：
ΔCpn＝ΔCp/(1-w)
χim＝(ΔCp0-ΔCpn)/ΔCp0 A differential scanning calorimeter was used to test and analyze the binder content of rubber composite materials. All test conditions were carried out at temperatures between -80°C and 25°C, with a heating rate of 5°C/min. The binder content of rubber composite materials is calculated according to the following formula:
ΔC pn =ΔC p /(1-w)
χ im =(ΔC p0 -ΔC pn )/ΔC p0
式中：ΔCp是橡胶在玻璃化转变温度下的热容量跳跃，ΔCpn是橡胶复合材料在填料填充下热容差的归一化处理值；w是橡胶复合材料中填料的重量分数；ΔCp0是未填充橡胶基体的玻璃化转变温度下的跳转热容量；χim是结合胶含量。In the formula: ΔC p is the heat capacity jump of the rubber at the glass transition temperature, ΔC pn is the normalized value of the heat tolerance of the rubber composite when filled with fillers; w is the weight fraction of the filler in the rubber composite; ΔC p0 is the jump heat capacity at the glass transition temperature of the unfilled rubber matrix; χ im is the binder content.
图6(a)显示，相同氧化石墨烯添加量时，当GO层间是静电力作用时，即本发明制备的橡胶复合材料的交联密度远远大于层间存在氢键(对比例1)和化学键结合(对比例2)的橡胶复合材料的交联密度。图6(b)表明，相较于GO层间存在氢键(对比例1)和化学键作用力(对比例2)，当GO层间存在静电力作用时(本发明)，制备的石墨烯/橡胶复合材料中，石墨烯固定的橡胶分子链的比例要大得多。这也很直观地表明，GO层间的静电力为一种可逆力，在动态运动的过程中，能够很大程度的使填料缠结大量的橡胶分子链并且使填料与橡胶基体间的界面相互作用增强。Figure 6(a) shows that when the same amount of graphene oxide is added, when there is an electrostatic force between the GO layers, that is, the cross-linking density of the rubber composite prepared by the present invention is much greater than the hydrogen bonds between the layers (Comparative Example 1) Cross-link density of rubber composites combined with chemical bonds (Comparative Example 2). Figure 6(b) shows that compared to the presence of hydrogen bonds (Comparative Example 1) and chemical bond forces (Comparative Example 2) between GO layers, when there are electrostatic forces between GO layers (the present invention), the prepared graphene/ In rubber composites, the proportion of rubber molecular chains anchored by graphene is much larger. This also intuitively shows that the electrostatic force between GO layers is a reversible force. During the dynamic movement process, the filler can entangle a large number of rubber molecular chains to a large extent and make the interface between the filler and the rubber matrix interact with each other. Enhanced effect.
(7)对实施例和对比例得到的天然橡胶硫化胶进行导热、磨耗和力学性能的测试。 导热性能的测试标准为GB/T3399，磨耗性能的测试标准为GB/T9867-2008，力学性能的测试标准为ISO37-2005，拉伸速率为500mm/min，撕裂速度为500mm/min。(7) Test the thermal conductivity, abrasion and mechanical properties of the natural rubber vulcanized rubber obtained in the Examples and Comparative Examples. The testing standard for thermal conductivity is GB/T3399, the testing standard for abrasion performance is GB/T9867-2008, the testing standard for mechanical properties is ISO37-2005, the tensile rate is 500mm/min, and the tearing speed is 500mm/min.
表2各实施例和对比例制备的天然橡胶复合材料的性能测试结果
Table 2 Performance test results of natural rubber composite materials prepared in various examples and comparative examples
由表2可以看出：本发明工艺制备的力学、导热和耐磨性能同时提升的石墨烯/天然橡胶硫化胶的力学性能均优于相同石墨烯含量的石墨烯层间为氢键(对比例1)和化学键结合(对比例2)的橡胶复合材料的力学性能。It can be seen from Table 2 that the mechanical properties of the graphene/natural rubber vulcanized rubber prepared by the process of the present invention with simultaneously improved mechanical, thermal conductivity and wear resistance properties are better than those of the same graphene content with hydrogen bonds between the graphene layers (Comparative Example 1) Mechanical properties of rubber composite materials combined with chemical bonds (Comparative Example 2).
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。 Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, but not to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features can be equivalently replaced; and these modifications or substitutions do not deviate from the essence of the corresponding technical solutions from the technical solutions of the embodiments of the present invention. scope.

Claims (8)

  1. 一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法，其特征在于，包括以下步骤：A method for preparing graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties, which is characterized by including the following steps:
    (一)通过静电相互作用使二氧化硅负载在氧化石墨烯表面：将硅烷偶联剂KH550加入到水与乙醇的共混溶液中，分散均匀后得到硅烷偶联剂水解液；将二氧化硅加入到水与乙醇的共混溶液中，分散均匀后加入硅烷偶联剂水解液，一定温度下反应一段时间，抽滤、洗涤、干燥，得到氨基化改性二氧化硅粉末；(1) Load silica on the surface of graphene oxide through electrostatic interaction: Add silane coupling agent KH550 to the blended solution of water and ethanol, and disperse it evenly to obtain a silane coupling agent hydrolyzate; add silica Add to the blended solution of water and ethanol, disperse evenly, add the silane coupling agent hydrolyzate, react at a certain temperature for a period of time, filter, wash and dry to obtain amination modified silica powder;
    将氨基化改性二氧化硅粉末加入到去离子水中并超声至分散均匀，然后滴加柠檬酸溶液，超声处理一定时间后，经多次离心、洗涤至分散液pH值为7，得到氨基质子化二氧化硅分散液，将其加入到氧化石墨烯水分散液中，超声处理一定时间，得到通过静电相互作用负载二氧化硅的氧化石墨烯的水分散液；Add aminated modified silica powder to deionized water and sonicate until dispersed evenly, then add citric acid solution dropwise, and after ultrasonic treatment for a certain period of time, centrifuge and wash multiple times until the pH value of the dispersion is 7 to obtain amino protons The silica dispersion is added to the graphene oxide aqueous dispersion, and ultrasonic treatment is performed for a certain period of time to obtain a graphene oxide aqueous dispersion loaded with silica through electrostatic interaction;
    (二)水相协同聚沉工艺制备通过静电相互作用负载二氧化硅的氧化石墨烯/天然橡胶母胶：将去离子水加入到天然胶乳中，然后加入通过静电相互作用负载二氧化硅的氧化石墨烯的水分散液，均匀分散后得到混合乳液；加入絮凝剂，则负载二氧化硅的氧化石墨烯粒子和天然胶乳中的橡胶颗粒会以π-π作用力相互吸附，在水相中有序集聚并协同沉淀出来，得到生胶，水洗、除水、烘干，则得到通过静电相互作用负载二氧化硅的氧化石墨烯/天然橡胶母胶；(2) Preparation of graphene oxide/natural rubber masterbatch loaded with silica through electrostatic interaction by aqueous synergistic coagulation process: Add deionized water to natural rubber latex, and then add oxidized graphene oxide loaded with silica through electrostatic interaction. The aqueous dispersion of graphene is uniformly dispersed to obtain a mixed emulsion; when a flocculant is added, the graphene oxide particles loaded with silica and the rubber particles in the natural latex will adsorb each other through π-π forces, and there is The raw rubber is obtained by sequential aggregation and cooperative precipitation. After washing, removing water and drying, a graphene oxide/natural rubber masterbatch loaded with silica through electrostatic interaction is obtained;
    (三)力学、导热和耐磨性能同时提升的石墨烯/天然橡胶硫化胶的制备：往步骤(二)制备的通过静电相互作用负载二氧化硅的改性氧化石墨烯/天然橡胶母胶中依次加入防老剂、抗氧化剂、活化剂及软化剂，密炼，分散均匀后得到混炼胶；往混炼胶中加入硫化促进剂和硫化剂，然后进行开炼，混合均匀后，薄通至胶料无气泡，停放一定时间后将其放置于模具中，于一定温度和一定压力下硫化一定时间，得到力学、导热和耐磨性能同时提升的石墨烯/天然橡胶硫化胶。(3) Preparation of graphene/natural rubber vulcanized rubber with improved mechanical, thermal conductivity and wear resistance properties: Add the modified graphene oxide/natural rubber masterbatch loaded with silica through electrostatic interaction prepared in step (2) Add anti-aging agent, antioxidant, activator and softener in sequence, mix and disperse evenly to obtain a rubber mixture; add vulcanization accelerator and vulcanizing agent to the rubber mixture, and then start kneading. After mixing evenly, pass it to a thin layer. The rubber has no bubbles. After it has been parked for a certain period of time, it is placed in the mold and vulcanized for a certain period of time at a certain temperature and pressure to obtain graphene/natural rubber vulcanized rubber with improved mechanical, thermal conductivity and wear resistance properties.
  2. 根据权利要求1所述的一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法，其特征在于，步骤(一)中，水与乙醇按照1:1-3的体积比制备共混溶液；所述硅烷偶联剂KH550用量为二氧化硅质量的5-15％；反应温度为65-85℃，反应时间为4-8h；干燥温度为50-70℃。A method for preparing graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties according to claim 1, characterized in that in step (1), water and ethanol are in a volume ratio of 1:1-3 Prepare a blended solution; the dosage of the silane coupling agent KH550 is 5-15% of the mass of silica; the reaction temperature is 65-85°C, the reaction time is 4-8h; the drying temperature is 50-70°C.
  3. 根据权利要求1所述的一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法，其特征在于，步骤(一)中，氨基化改性二氧化硅粉末在去离子水中的浓度为50-300mg/mL，柠檬酸溶液的浓度为1.5-4mol/L。 A method for preparing graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties according to claim 1, characterized in that in step (1), amination modified silica powder is dissolved in deionized water The concentration of citric acid solution is 50-300mg/mL, and the concentration of citric acid solution is 1.5-4mol/L.
  4. 根据权利要求1所述的一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法，其特征在于，步骤(一)中，氧化石墨烯水分散液的溶度是0.5-10mg/mL。A method for preparing graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties according to claim 1, characterized in that in step (1), the solubility of the graphene oxide aqueous dispersion is 0.5- 10mg/mL.
  5. 根据权利要求1所述的一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法，其特征在于，步骤(一)中，氨基化改性二氧化硅粉末与柠檬酸的质量比为1-3:0.5-1；得到的通过静电相互作用负载二氧化硅的氧化石墨烯中氧化石墨烯与二氧化硅的质量比为1:10-60。A method for preparing graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties according to claim 1, characterized in that in step (1), the mixture of amination modified silica powder and citric acid The mass ratio is 1-3:0.5-1; the mass ratio of graphene oxide to silicon dioxide in the obtained graphene oxide loaded with silicon dioxide through electrostatic interaction is 1:10-60.
  6. 根据权利要求1所述的一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法，其特征在于，步骤(一)中，超声分散的功率为50-300W。A method for preparing graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties according to claim 1, characterized in that in step (1), the power of ultrasonic dispersion is 50-300W.
  7. 根据权利要求1所述的一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法，其特征在于，步骤(二)中，将去离子水加入到天然胶乳使天然胶乳乳液的浓度为10-40wt.％，所述絮凝剂的浓度为10wt.％，絮凝剂与天然橡胶的质量比为2-6:100。A method for preparing graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties according to claim 1, characterized in that in step (2), deionized water is added to the natural rubber latex to form a natural rubber latex emulsion. The concentration of the flocculant is 10-40wt.%, the concentration of the flocculant is 10wt.%, and the mass ratio of the flocculant to natural rubber is 2-6:100.
  8. 根据权利要求1所述的一种力学、导热和耐磨性能同时提升的石墨烯/天然橡胶的制备方法，其特征在于，步骤(三)中，所述防老剂、抗氧化剂、活化剂、软化剂、硫化促进剂、硫化剂的质量比为1:1:5:2:2:2。 A method for preparing graphene/natural rubber with simultaneously improved mechanical, thermal conductivity and wear resistance properties according to claim 1, characterized in that in step (3), the antioxidant, antioxidant, activator, softener The mass ratio of agent, vulcanization accelerator and vulcanizing agent is 1:1:5:2:2:2.
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