CN114891281A - Simplified method for simultaneously optimizing mechanics, low heat generation and wear resistance of graphene modified natural rubber vulcanized rubber - Google Patents
Simplified method for simultaneously optimizing mechanics, low heat generation and wear resistance of graphene modified natural rubber vulcanized rubber Download PDFInfo
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Abstract
The invention relates to the field of graphene and functional rubber composite materials thereof, in particular to a simplifying method for simultaneously optimizing the mechanics, low heat generation and wear resistance of graphene modified natural rubber vulcanized rubber; firstly, reducing the number of oxygen-containing functional groups on the surface of a graphene oxide sheet layer by a simplified modification process easy for industrial production, and then preparing graphene modified natural rubber vulcanized rubber with optimized mechanical, low-heat generation and wear-resisting properties by using a water-phase synergistic coagulation process and a mechanical blending method; the water phase synergistic coagulation process and the mechanical blending method can enable the modified graphene oxide with the reduced number of the oxygen-containing functional groups on the surface to be uniformly dispersed in the natural rubber vulcanized rubber, and the modified graphene oxide with the reduced number of the oxygen-containing functional groups on the surface can enable the crosslinking density of the natural rubber vulcanized rubber to be increased and the crosslinking network to be more perfect, so that the graphene modified natural rubber vulcanized rubber with optimized mechanical, low-heat generation and wear-resisting properties is obtained. The method has important significance for promoting the application of the graphene in the field of high-performance rubber.
Description
Technical Field
The invention relates to the field of graphene and functional rubber composite materials thereof, in particular to a simplifying method for simultaneously optimizing the mechanics, low heat generation and wear resistance of graphene modified natural rubber vulcanized rubber.
Background
Natural Rubber (NR) has excellent mechanical properties, tear resistance, elasticity, and the like, and is widely used in the fields of automobile tires, electric wires, cables, and the like. However, natural rubber requires the addition of fillers to achieve its various functions, including high modulus, high tear resistance, and high thermal conductivity. In addition, in order to manufacture a rubber composite material with excellent comprehensive performance, nanoparticles with characteristics of small size, large surface area and the like become an ideal choice for the rubber matrix reinforcing filler, wherein the representative materials mainly comprise nano carbon black, carbon nano tubes, nano montmorillonite, graphene and the like.
The graphene is sp 2 The new material with a single-layer two-dimensional honeycomb lattice structure formed by tightly stacking hybridized and connected carbon atoms has excellent optical, electrical and mechanical properties, has important application prospects in the fields of materials, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future. Graphene Oxide (GO) is a two-dimensional (2D) material with various oxygen-containing functional groups obtained by oxidizing graphite by means of physical chemistry and the like, and is an economic way for mass production of graphene. Graphene and derivatives thereof have excellent mechanical strength and conductivityAnd thermal conductivity, which is widely applied to reinforcing modified rubber, so that the prepared rubber composite material has better mechanical strength, toughness and thermal conductivity.
The mechanical property is directly reflected by the construction of the rubber cross-linked network and the dispersion condition of the filler. The compression heat buildup of rubber composites is associated with the disruption and reestablishment of their filler network, the friction between rubber molecular chains, and the disruption and rearrangement of the crosslinked network structure. Under the action of dynamic load, the stronger cross-linked network can limit the filler and prevent the rubber macromolecular chains from sliding off the surface of the filler. The abrasion of rubber is related to its own resistance, mechanical properties, filler network structure and cross-linked network structure. Therefore, the key to realize the improvement of the rubber performance is to construct a more perfect crosslinking network. The obtained composite material with excellent mechanical properties can expand the application range of rubber, the excellent heat generation property can reduce the heat accumulation of the rubber in the using process, and the excellent wear resistance property can prolong the service life of the rubber.
In a plurality of processes for preparing the filler/natural rubber, the emulsion blending method has remarkable advantages, can improve the dispersibility of the filler, is convenient for realizing continuous mixing, and can shorten the mixing time, reduce the mixing energy consumption, reduce the dust pollution and the like.
Disclosure of Invention
The invention aims to provide a simplified method for simultaneously optimizing the mechanics, low heat generation and wear resistance of graphene modified natural rubber vulcanized rubber.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a simplified method for simultaneously optimizing the mechanical property, low heat generation and wear resistance of graphene modified natural rubber vulcanized rubber is characterized in that firstly, the number of oxygen-containing functional groups on the surface of a graphene oxide sheet layer is reduced through a simplified modification process easy for industrial production, and then the graphene modified natural rubber vulcanized rubber with the simultaneously optimized mechanical property, low heat generation and wear resistance is prepared by utilizing a water-phase synergetic coagulation process and a mechanical blending method; the aqueous phase synergistic coagulation process and the mechanical blending method can enable the modified graphene oxide with the reduced surface oxygen-containing functional group number to be uniformly dispersed in the natural rubber vulcanized rubber, and the modified graphene oxide with the reduced surface oxygen-containing functional group number can effectively reduce the adsorption of the graphene to a vulcanization aid in a natural rubber composite material system, so that the crosslinking rate and the vulcanization rate of the natural rubber composite material can be improved, the crosslinking density of the vulcanized natural rubber vulcanized rubber is increased, the crosslinking network is more perfect, and the graphene modified natural rubber vulcanized rubber with the mechanical property, the low heat generation property and the wear resistance property optimized simultaneously is obtained.
A simplified method for simultaneously optimizing the mechanics, low heat generation and wear resistance of graphene modified natural rubber vulcanized rubber specifically comprises the following steps:
adding a reducing agent into water, fully dissolving, adding the graphene oxide aqueous dispersion, and reacting for a certain time at a certain temperature to obtain a modified graphene oxide aqueous dispersion with the surface oxygen-containing functional groups effectively reduced in number;
preparing modified graphene oxide/natural rubber master batch by a water phase synergistic coagulation process: adding deionized water into natural latex, then adding the modified graphene oxide aqueous dispersion, fully stirring and mixing to obtain uniformly dispersed mixed emulsion; adding a flocculating agent, so that the modified graphene oxide particles and the rubber particles in the natural latex can be mutually adsorbed by pi-pi acting force, orderly aggregated in a water phase and synergistically precipitated to obtain raw rubber; washing, dewatering and drying the obtained crude rubber to obtain modified graphene oxide/natural rubber master batch;
preparing the graphene modified natural rubber vulcanized rubber with optimized mechanical, low heat generation and wear resistance performance: sequentially adding an anti-aging agent, an antioxidant, an activating agent and a softening agent into the modified graphene oxide/natural rubber master batch prepared in the step two, banburying, and uniformly dispersing to obtain a rubber compound; adding a vulcanization accelerator and a vulcanizing agent into the rubber compound, then carrying out open milling, after uniformly mixing, thinly passing the rubber compound until no air bubbles exist, placing the rubber compound in a mold after standing for a certain time, and vulcanizing the rubber compound for a certain time at a certain temperature and under a certain pressure to obtain the graphene modified natural rubber vulcanized rubber with optimized mechanical property, low heat generation and wear resistance.
As a further improvement of the technical scheme of the invention, the proportion of the used raw materials is as follows: 100 parts of natural rubber, 0.1-5 parts of modified graphene oxide particles and 11-13 parts of rubber additives.
As a further improvement of the technical scheme of the invention, in the step (i), the reducing agent is at least one of hydrazine hydrate, ascorbic acid, lithium aluminum hydride, iodine and sodium bisulfite; the reaction temperature is 60-120 ℃, and the reaction time is 2-6 h; the concentration of the obtained modified graphene oxide aqueous dispersion is 0.5-10 mg/mL -1 。
As a further improvement of the technical scheme of the invention, in the step (II), the flocculating agent is at least one of a calcium chloride solution, a sodium chloride solution, a potassium chloride solution, a sodium sulfate solution, a hydrochloric acid solution and a formic acid solution.
As a further improvement of the technical scheme of the invention, in the second step, deionized water is added into the natural latex to make the concentration of the natural latex emulsion be 10-40 wt.%; the concentration of the flocculant is 10wt.%, and the mass ratio of the flocculant to the natural rubber is 2-6: 100.
As a further improvement of the technical scheme of the invention, in the third step, the mass ratio of the anti-aging agent, the antioxidant, the activator, the softener, the vulcanization accelerator and the vulcanizing agent is 1:1:5:2:2: 2.
As a further improvement of the technical scheme of the invention, in the step (III), the vulcanization accelerator is N-tert-butyl-2-benzothiazole sulfonamide, N-cyclohexyl-2-benzothiazole sulfonamide or N- (oxydiethylene) -2-benzothiazole sulfonamide; the vulcanizing agent is sulfur or sulfur monochloride; the anti-aging agent is 2, 6-di-tert-butyl-4-methylphenol, 2, 4-trimethyl-1, 2-dihydroquinoline polymer or 2-thiol benzimidazole; the antioxidant is N-isopropyl-N' -phenyl-p-phenylenediamine, p-phenylaniline or dilauryl thiodipropionate; the activating agent is zinc gluconate, zinc oxide or magnesium oxide; the softening agent is stearic acid, dibutyl titanate or dioctyl adipate.
As a further improvement of the technical scheme of the invention, in the step III, the mixing temperature of the internal mixer is 105-120 ℃, and the mixing time is 3-5 min; the open milling temperature is 50-70 ℃, and the open milling time is 8-12 min; the standing time of the mixed rubber is 18-36 h; the vulcanization temperature is 135 ℃ and 170 ℃, the vulcanization pressure is 10-30MPa, and the vulcanization time is 10-25 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the quantity of oxygen-containing functional groups on the surface of the graphene oxide sheet layer is reduced by using a simplified modification process which is easy for industrial production, so that the adsorption of modified graphene oxide on a vulcanization assistant in a composite material system is weakened, the crosslinking rate and the vulcanization rate of the natural rubber composite material are improved, the crosslinking density of the natural rubber vulcanized rubber is increased, the crosslinking network is more perfect, the interface interaction between the modified graphene oxide sheet and the matrix natural rubber is improved, and finally the natural rubber vulcanized rubber with optimized mechanical, low-heat generation and wear-resisting properties is obtained.
(2) The oxygen-containing functional groups on the surface of the graphene oxide sheet layer have important influence on the dispersibility of the graphene in the natural rubber latex and further in the finally prepared natural rubber vulcanized rubber, and the more the number of the oxygen-containing functional groups is, the better the dispersibility of the graphene in the natural rubber latex and further in the finally prepared natural rubber vulcanized rubber is; according to the invention, through a water-phase synergistic coagulation process and a mechanical blending method, the problem that the modified graphene oxide is difficult to disperse and homogenize in the natural rubber vulcanized rubber and further in the finally prepared natural rubber vulcanized rubber due to the fact that the number of oxygen-containing functional groups on the surfaces of lamellae is reduced is effectively solved, and in addition, the modified graphene oxide with the reduced number of oxygen-containing functional groups on the surfaces can increase the crosslinking density of the natural rubber vulcanized rubber and improve the crosslinking network, so that the natural rubber vulcanized rubber with optimized mechanical, low-heat generation and wear-resisting properties is obtained.
(3) The preparation process is simple, green and environment-friendly, has no harsh requirements, and relates to conventional equipment, so that the preparation process is easy for industrial production and has important significance for promoting the application of graphene in the field of high-performance rubber.
Drawings
Fig. 1 XPS spectra of graphene oxide prepared in examples 1 to 3 and comparative example 2. Wherein (a) is a full spectrum and (b) - (e) are fitted curves of the spectrum of C1 s.
FIG. 2 vulcanization curves of mechanically, low heat build and abrasion resistance simultaneously optimized natural rubber vulcanizates prepared in examples 1-3 and comparative examples 1-2, Table 1 summarizes the vulcanization characteristics of rGO/NR composites with modified graphene oxide rGO having different numbers of oxygen-containing functional groups.
FIG. 3 relaxation time curves for mechanical, low heat generation, and abrasion resistance properties of simultaneously optimized natural rubber vulcanizates prepared in examples 1-3 and comparative examples 1-2.
FIG. 4 crosslink density of the mechanically, low heat generation, and abrasion resistance properties of the simultaneously optimized natural rubber vulcanizates prepared in examples 1-3 and comparative examples 1-2.
FIG. 5 DSC curves of mechanically, low heat build and abrasion resistant simultaneously optimized natural rubber vulcanizates prepared in examples 1-3 and comparative examples 1-2.
FIG. 6 (a) stress-strain curve and (b) Mooney-Rivlin curve of a natural rubber vulcanizate prepared in examples 1-3 and comparative examples 1-2 with simultaneously optimized mechanical, low heat generation and abrasion resistance properties.
Detailed Description
The present invention is further illustrated by the following specific examples.
Examples 1 to 3
A simplified method for simultaneously optimizing the mechanics, low heat generation and wear resistance of graphene modified natural rubber vulcanized rubber comprises the following specific steps in embodiments 1-3:
firstly, a graphene oxide simplified modification process for effectively reducing the number of oxygen-containing functional groups on the surface: adding 1g, 2g and 3g of reducing agent ascorbic acid into water, stirring for 10min, mixing, and adding graphene oxide dispersion (200 mL, 5 mg. mL) -1 ) Stirring and reacting for 3 hours at 95 ℃ to obtain modified graphene oxide aqueous dispersion liquid with different oxygen-containing functional group numbers on the surface, wherein 1g of modified graphene oxide obtained in example 1 is characterized as rGO-1, 2g of modified graphene oxide obtained in example 2 is characterized as rGO-2, and 3g of modified graphene oxide obtained in example 3 is characterized as rGO-3;
(ii) aqueous phase cooperative polymerizationPreparing modified graphene oxide/natural rubber master batch by using a precipitation process: adding a certain amount of deionized water into natural latex (167 g, 60 wt.%), stirring until uniform to obtain a natural latex emulsion with a concentration of 20 wt.%, and adding the modified graphene oxide aqueous dispersion (200 mL, 5 mg. mL) prepared in the step (I) -1 ) Fully stirring and mixing to obtain uniformly dispersed mixed emulsion; adding 10wt.% of CaCl into the flocculant 2 25g of the solution, so that the modified graphene oxide particles and the rubber particles are orderly aggregated and synergistically precipitated in the water phase; washing the obtained crude rubber with water, removing water, and drying in a 65 ℃ oven to constant weight to obtain modified graphene oxide/natural rubber master batch;
preparing the natural rubber vulcanized rubber with the mechanical property, the low heat generation property and the wear resistance optimized simultaneously: 100g of modified graphene oxide/natural rubber master batch is placed in an internal mixer and mixed under the conditions of 110 ℃ and 40rpm, 1g of antioxidant 4010NA, 1g of antioxidant RD, 5g of activator ZnO and 2g of softener SA are added in three times during the mixing, the mixing is carried out for 4min each time, and the rubber material is discharged. And cooling the rubber material to room temperature, transferring the rubber material to an open mill, opening at 60 ℃, uniformly dispersing, adding 2g of vulcanization accelerator NOBS and 1g of sulfur, uniformly mixing, and thinly introducing the rubber material until the rubber material has no bubbles. After the rubber is stopped for 24 hours, the rubber compound is vulcanized for a certain time (t) by a vulcanizer at 150 ℃ and 15MPa C90 ) To obtain a natural rubber vulcanizate with simultaneous optimization of multiple properties, wherein t C90 Measured by a Rubber Processing Analyzer (RPA). The multi-property simultaneous optimization natural rubber vulcanizates obtained in examples 1,2, and 3 are denoted as rGO-1/NR, rGO-2/NR, and rGO-3/NR, respectively. The formulations of the examples are shown in Table 1.
Comparative example 1: (Natural rubber vulcanizate)
The specific procedure in comparative example 1 was:
firstly, none;
preparing natural rubber master batch: adding a certain amount of deionized water into natural latex (167 g, 60 wt.%), and stirring until the mixture is uniformly dispersed to obtain a latex solution with the concentration of 20 wt.%; adding 10wt.% of CaCl into the flocculant 2 25g of the solution; washing the obtained crude rubber with water, removing water, and drying in a 65 ℃ oven to constant weight to obtain natural rubber master batch;
③ same as examples 1 to 3. The formulation is shown in Table 1.
Comparative example 2: (graphene oxide/Natural rubber vulcanizate)
The specific procedure in comparative example 2 was:
preparing the graphene oxide/natural rubber composite material: the same procedure as in the second step of examples 1 to 3 is carried out except that the modified graphene oxide particles in the second step of examples 1 to 3 are replaced with graphene oxide particles.
③ same as examples 1 to 3. The formulation is shown in Table 1.
TABLE 1 formulation tables for examples 1-3 and comparative examples 1-2
Fig. 1 is XPS spectra of the modified graphene oxides prepared in examples 1 to 3 and the graphene oxide prepared in comparative example 2. As can be seen from FIG. 1 (a), the intensity of the O1s peak decreases with increasing degree of reduction, indicating a steady decrease in the oxygen content. In fig. 1 (b) - (e), the major peak at 284.7 eV is assigned to the C-C bond, 285.5 eV to the C-O bond, 286.8 eV to the C = O bond, and 288.8 eV to the O-C = O bond. It can be seen that the relative intensity of the peak corresponding to the oxygen-containing group of the modified graphene oxide is significantly reduced from that of the C peak, particularly the peaks of C = O and C — O, as the degree of reduction increases. The O/C ratio is extracted from the XPS spectrum, the unmodified graphene oxide GO prepared in the comparative example 2 is 0.44, the modified graphene oxide rGO-1 prepared in the example 1 is 0.24, the modified graphene oxide rGO-2 prepared in the example 2 is 0.19, and the modified graphene oxide rGO-3 prepared in the example 3 is 0.18, which indicates that the modified graphene oxide rGO with different oxygen-containing functional group numbers is successfully prepared.
FIG. 2 shows a natural rubber compositeThe vulcanization profile, table 2, summarizes the vulcanization characteristics of the natural rubber composite. The addition of the unmodified graphene oxide prepared in comparative example 2 extended the scorch time (t) compared to the pure rubber of comparative example 1 s2 ) And vulcanization time (t) c90 ) Resulting in a delay in the vulcanization reaction and inhibition of vulcanization of the rubber. However, the scorch time and cure time of the natural rubber vulcanizate were reduced by incorporation of the modified graphene oxide rGO prepared in examples 1-3, indicating that the modified graphene oxide rGO prepared in examples 1-3 can promote the vulcanization of the natural rubber vulcanizate. The reason is that: the surface of the unmodified graphene oxide GO prepared in the comparative example 2 shows weak acidity, and the activating agent and the accelerating agent in the natural rubber vulcanized rubber system are adsorbed by abundant polar oxygen-containing groups on the surface of the natural rubber vulcanized rubber system, so that the chemical crosslinking of the prepared natural rubber composite GO/NR is reduced. The modified graphene oxide rGO prepared in the embodiments 1-3 can be used as a reaction point for physical crosslinking of natural rubber, so that the crosslinking rate of vulcanized natural rubber can be increased. In the crosslinking reaction, the faster crosslinking speed and the higher vulcanization rate index (CRI) can lead the rubber phase to adsorb the vulcanization auxiliary agent through a plurality of mechanisms such as acid-base action, hydrogen bonds or charge transfer and the like to form a stronger crosslinking network. In Table 2, the maximum torque (M) of the natural rubber composite H ) The value increases with the addition of rGO with a higher degree of reduction. After further analysis, the minimum torque and the maximum torque (M) are found H -M L ) The torque difference between also increases significantly with increasing degree of reduction of the added rGO. These results indicate that the modified graphene oxide with the effectively controlled amount of surface oxygen-containing functional groups can cause the increase of the crosslinking density of the natural rubber composite material and the further development of the crosslinking network.
TABLE 2 vulcanization characteristics of Natural rubber composites of examples and comparative examples
FIG. 3 is a graph of relaxation time for a natural rubber vulcanizate prepared with simultaneous optimization of mechanical, low heat generation, and abrasion resistance properties. Through LF-NMR test, a relaxation hysteresis curve of H atom vibration in an organic molecular chain can be obtained firstly. And then through data inversion, the relaxation time and the content of soft and hard segments in the rubber can be obtained. Since the rubber is more constrained by the crosslinked network and the relaxation time is shorter in the hard segment, the relaxation time of the soft segment of the rubber is larger and the sum of their peak areas is 100%. With the addition of rGO with increasing degree of reduction prepared in examples 1-3, the relaxation time corresponding to the hard segment of the rubber was continuously reduced and the peak area ratio was continuously increased, indicating that the interfacial effect between the filler and the rubber was continuously enhanced and the crosslinked network was also continuously perfected.
FIG. 4 is a graph of the crosslink density of a natural rubber vulcanizate prepared with simultaneous optimization of mechanical, low heat build up, and abrasion resistance properties. Compared with the comparative examples 1 and 2, the crosslinking density of the composite materials prepared in the examples 1 to 3 is obviously improved, and the crosslinking density of the rubber composite material is increased and the crosslinking network is more perfect along with the increase of the reduction degree of rGO, namely the reduction of the number of oxygen-containing functional groups on the surface of the modified graphene oxide.
FIG. 5 is a DSC curve of a natural rubber vulcanizate prepared with simultaneous optimization of mechanical, low heat build up, and abrasion resistance properties. DSC testing can determine the interaction that forms between the natural rubber matrix and the GO filler, as the presence of the filler typically results in a change in the glass transition temperature of the elastomeric compound. The multifunctionality prepared in examples 1-3 simultaneously optimized natural rubber vulcanizates had slightly increased glass transition temperature values compared to comparative examples 1 and 2 due to increased interaction between the filler and the macromolecular chains of the natural rubber and the increased cross-linking network restricting movement of the rubber segments. This is the same trend as the increase in crosslink density.
FIG. 6 (a) shows a typical stress-strain curve for a natural rubber vulcanizate with mechanical, low heat build up and abrasion resistance properties optimized simultaneously. In comparative example 1, when the strain is less than 700%, the stress of the pure natural rubber increases slowly; but when the strain reaches 700%, its stress increases sharply until the specimen cracks. This is due to the strain induced crystallization of the pure natural rubber chains in the direction of the stress during stretching. In comparative example 2 and examples 1 to 3, as the filler was added to the natural rubber, the strain inducing crystallization was shifted to a low strain direction. In example 3, when 1 part of the prepared modified graphene oxide rGO-3 is added, the strain of induced crystallization of rGO-3/NR is 550%. This is mainly due to the strong cross-linked network causing high interfacial interactions between rGO and NR weakening the entanglement between NR molecular chains, allowing the molecular chains to orient and crystallize in the stretched state.
To better analyze the interaction between the filler and the matrix, the Mooney-Rivlin equation was used to evaluate the multi-properties while optimizing the stress-strain curve of the natural rubber vulcanizate. It is represented by equation (1).
Wherein: δ is the tensile strength during measurement divided by the stress of the undeformed specimen cross section, λ is the elongation of the deformed specimen divided by the length of the undeformed specimen, C 1 And C 2 Is a constant of two materials, independent of λ. The curves obtained are shown to be "U" shaped, and the upward shift of the Mooney-Rivlin curve indicates the enhancement of the interaction between the filler and the rubber matrix, which can be used to evaluate the limited elongation of the rubber chain and the interfacial adhesion between the filler and the matrix. Fig. 6 (b) shows that with the addition of the prepared modified graphene oxide rGO with a higher degree of reduction, the inflection point of the curve rises to a larger λ -1 It is demonstrated that the properties of the blends prepared in examples 1-3 are optimized simultaneously to provide a stronger interface between the filler and the rubber in the natural rubber vulcanizate.
The natural rubber vulcanizates obtained in the examples and comparative examples were tested for heat generation, abrasion, and mechanical properties. The test standard of the heat generating performance is GB/T1687.1-2016, the test standard of the abrasion performance is GB/T9867-. The results of the performance tests are shown in Table 3.
TABLE 3 test results of mechanical, heat generation and abrasion resistance of the vulcanized natural rubber prepared in examples 1 to 3 and comparative examples 1 to 2
As can be seen from Table 3, the natural rubber vulcanizate prepared by the invention and optimized in mechanical, low heat generation and wear resistance properties has the characteristics of low abrasion, small heat generation in compression and excellent mechanical properties.
Claims (9)
1. A simplified method for simultaneously optimizing the mechanical property, low heat generation and wear resistance of graphene modified natural rubber vulcanized rubber is characterized in that firstly, the number of oxygen-containing functional groups on the surface of a graphene oxide sheet layer is reduced through a simplified modification process easy for industrial production, and then the graphene modified natural rubber vulcanized rubber with the simultaneously optimized mechanical property, low heat generation and wear resistance is prepared by utilizing a water-phase synergetic coagulation process and a mechanical blending method; the aqueous phase synergistic coagulation process and the mechanical blending method can enable the modified graphene oxide with the reduced surface oxygen-containing functional group number to be uniformly dispersed in the natural rubber vulcanized rubber, and the modified graphene oxide with the reduced surface oxygen-containing functional group number can effectively reduce the adsorption of the graphene to a vulcanization aid in a natural rubber composite material system, so that the crosslinking rate and the vulcanization rate of the natural rubber composite material can be improved, the crosslinking density of the natural rubber vulcanized rubber is increased, the crosslinking network is more complete, and the graphene modified natural rubber vulcanized rubber with the optimized mechanical, low-heat generation and wear-resisting properties is obtained.
2. The simplified method for simultaneously optimizing mechanical, low heat generation and wear resistance properties of graphene-modified natural rubber vulcanizate according to claim 1, comprising the steps of:
adding a reducing agent into water, fully dissolving, adding the graphene oxide aqueous dispersion, and reacting for a certain time at a certain temperature to obtain a modified graphene oxide aqueous dispersion with the surface oxygen-containing functional groups effectively reduced in number;
preparing modified graphene oxide/natural rubber master batch by a water phase synergistic coagulation process: adding deionized water into natural latex, then adding the modified graphene oxide aqueous dispersion, and fully mixing to obtain uniformly dispersed mixed emulsion; adding a flocculating agent, so that the modified graphene oxide particles and the rubber particles in the natural latex can be mutually adsorbed by pi-pi acting force, and thus the modified graphene oxide particles and the rubber particles are orderly aggregated in a water phase and synergistically precipitated to obtain raw rubber; washing, dewatering and drying the obtained crude rubber to obtain modified graphene oxide/natural rubber master batch;
preparing the graphene modified natural rubber vulcanized rubber with optimized mechanical, low heat generation and wear resistance performance: sequentially adding an anti-aging agent, an antioxidant, an activating agent and a softening agent into the modified graphene oxide/natural rubber master batch prepared in the step two, banburying, and uniformly dispersing to obtain a rubber compound; adding a vulcanization accelerator and a vulcanizing agent into the rubber compound, then carrying out open milling, after uniformly mixing, thinly passing the rubber compound until no air bubbles exist, placing the rubber compound in a mold after standing for a certain time, and vulcanizing the rubber compound for a certain time at a certain temperature and under a certain pressure to obtain the graphene modified natural rubber vulcanized rubber with optimized mechanical property, low heat generation and wear resistance.
3. The simplified method for simultaneously optimizing the mechanical property, low heat generation and wear resistance of graphene modified natural rubber vulcanizate according to claim 2, wherein the raw materials are used in the following proportions: 100 parts of natural rubber, 0.1-5 parts of modified graphene oxide particles and 11-13 parts of rubber additives.
4. The simplified method for simultaneously optimizing the mechanical properties, low heat generation and wear resistance of graphene-modified natural rubber vulcanizate according to claim 2, wherein in step (r), the reducing agent is at least one of hydrazine hydrate, ascorbic acid, lithium aluminum hydride, iodine and sodium bisulfite; the reaction temperature is 60-120 ℃, and the reaction time is 2-6 h; the concentration of the obtained modified graphene oxide aqueous dispersion is 0.5-10 mg/mL -1 。
5. The simplified method for simultaneously optimizing the mechanical property, low heat generation property and wear resistance of graphene modified natural rubber vulcanized rubber according to claim 2, wherein in the step (II), the flocculating agent is at least one of a calcium chloride solution, a sodium chloride solution, a potassium chloride solution, a sodium sulfate solution, a hydrochloric acid solution and a formic acid solution.
6. The simplified method for simultaneously optimizing mechanical properties, low heat generation and wear resistance of graphene-modified natural rubber vulcanized rubber according to claim 2, wherein in the second step, deionized water is added to the natural rubber latex so that the concentration of the emulsion of the natural rubber latex is 10-40 wt.%, the concentration of the flocculant is 10wt.%, and the mass ratio of the flocculant to the natural rubber is 2-6: 100.
7. The simplified method for simultaneously optimizing the mechanics, low heat generation and wear resistance of graphene-modified natural rubber vulcanizate according to claim 2, wherein in step three, the mass ratio of the antioxidant, the activator, the softener, the vulcanization accelerator and the vulcanizing agent is 1:1:5:2:2: 2.
8. The simplified method for simultaneously optimizing mechanical, low heat generation and wear resistance properties of graphene modified natural rubber vulcanizate according to claim 2, wherein in step (iii), the vulcanization accelerator is N-tert-butyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide or N- (oxydiethylene) -2-benzothiazolesulfenamide; the vulcanizing agent is sulfur or sulfur monochloride; the anti-aging agent is 2, 6-di-tert-butyl-4-methylphenol, 2, 4-trimethyl-1, 2-dihydroquinoline polymer or 2-thiol benzimidazole; the antioxidant is N-isopropyl-N' -phenyl-p-phenylenediamine, p-phenylaniline or dilauryl thiodipropionate; the activating agent is zinc gluconate, zinc oxide or magnesium oxide; the softening agent is stearic acid, dibutyl titanate or dioctyl adipate.
9. The simplified method for simultaneously optimizing the mechanics, low heat generation and wear resistance of graphene modified natural rubber vulcanizate according to claim 2, characterized in that in step (c), the mixing temperature of the internal mixer is 105-; the open milling temperature is 50-70 ℃, and the open milling time is 8-12 min; the standing time of the mixed rubber is 18-36 h; the vulcanization temperature is 135 ℃ and 170 ℃, the vulcanization pressure is 10-30MPa, and the vulcanization time is 10-25 min.
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