CN115627018A - Preparation method of ageing-resistant high-elasticity rubber compound - Google Patents
Preparation method of ageing-resistant high-elasticity rubber compound Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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- C—CHEMISTRY; METALLURGY
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
The invention discloses a preparation method of an aging-resistant high-elasticity rubber compound, which comprises the following steps: s1, stirring and mixing a thermoplastic polyester elastomer, styrene butadiene rubber and ethylene acrylate rubber at 135-180 ℃ for 0.5-2h; s2, after the product obtained in the step S1 is cooled to 50-70 ℃, transferring the product into an open mill, adding polytetrafluoroethylene, stearic acid and modified multi-element filler into the open mill, and mixing for 5-20min at 65-85 ℃; s3, adding a vulcanizing agent and an auxiliary agent into the open mill, and mixing for 10-25min at 75-95 ℃ to obtain the aging-resistant high-elasticity rubber compound. The rubber compound prepared by the invention has excellent aging resistance and high elasticity, can overcome the defects of easy agglomeration and poor compatibility with an organic system of carbon fibers, nano zinc oxide and nano aluminum oxide, and can greatly improve the comprehensive performance of the rubber compound through the synergistic enhancement effect among the materials.
Description
Technical Field
The invention relates to the field of rubber materials, in particular to a preparation method of an aging-resistant high-elasticity rubber compound.
Background
Elasticity, aging resistance, mechanical strength and the like are important performance indexes of rubber, the rubber is always expected to have more excellent comprehensive performance when being applied so as to meet the requirements of various scenes, and the rubber with a single component is difficult to have good comprehensive performance. The comprehensive performance of the rubber can be improved by blending various rubbers and using some auxiliary fillers.
TPEE (thermoplastic polyester elastomer) is a block copolymer containing polyester hard segments and polyether soft segments, has the characteristics of high strength, good flexibility, high elasticity and the like, can be used for preparing sealing materials, damping materials and the like, but has the defects of insufficient elasticity, aging resistance and the like when a single TPEE is used, and the performance needs to be improved by compounding other materials. For example, CN105602041B discloses a high-hardness high-elasticity NBR/TPEE blend rubber and a preparation method thereof, which improves the comprehensive performance of the blend rubber by compounding NBR and TPEE. The inorganic filler can effectively improve the performance of the rubber, for example, the nano zinc oxide can effectively improve the toughness and the ageing resistance of the rubber, and the carbon fiber can improve the strength and the toughness of a rubber compound system. However, the fillers have the defects of easy agglomeration and poor compatibility with an organic system, so that the reinforcing effect is difficult to fully exert.
Therefore, there is a need for improvements in the art to provide a more reliable solution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of an aging-resistant high-elasticity rubber compound aiming at the defects in the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of an aging-resistant high-elasticity rubber compound comprises the following steps:
s1, stirring and mixing a thermoplastic polyester elastomer, styrene butadiene rubber and ethylene acrylate rubber at 135-180 ℃ for 0.5-2h;
s2, after the product obtained in the step S1 is cooled to 50-70 ℃, transferring the product into an open mill, adding polytetrafluoroethylene, stearic acid and modified multi-element filler into the open mill, and mixing for 5-20min at 65-85 ℃;
s3, adding a vulcanizing agent and an auxiliary agent into the open mill, and mixing for 10-25min at 75-95 ℃ to obtain the aging-resistant high-elasticity rubber compound.
Preferably, the raw materials for preparing the aging-resistant high-elasticity rubber compound comprise the following components in parts by weight:
28-44 parts of thermoplastic polyester elastomer;
45-86 parts of styrene butadiene rubber;
30-62 parts of ethylene acrylate rubber;
4-18 parts of polytetrafluoroethylene;
2-6.5 parts of stearic acid;
18-46 parts of modified multi-element filler;
2-6 parts of a vulcanizing agent;
3.5-18 parts of an auxiliary agent.
Preferably, the auxiliary agents include a vulcanization accelerator, an anti-aging agent, and a plasticizer.
Preferably, the raw materials for preparing the aging-resistant high-elasticity rubber compound comprise the following components in parts by weight:
28-44 parts of thermoplastic polyester elastomer;
45-86 parts of styrene butadiene rubber;
30-62 parts of ethylene acrylate rubber;
4-18 parts of polytetrafluoroethylene;
2-6.5 parts by weight of stearic acid;
18-46 parts of modified multi-element filler;
2-6 parts of a vulcanizing agent;
0.5-4 parts by weight of a vulcanization accelerator;
1-4 parts of anti-aging agent;
2-10 parts of plasticizer.
Preferably, the vulcanizing agent is bisphenol AF or vulcanizing agent DCP, the vulcanization accelerator is accelerator TMTD or accelerator TT, the anti-aging agent is one or a mixture of two of anti-aging agent 4010NA and anti-aging agent D, and the plasticizer is one or a mixture of more of dioctyl phthalate, dibutyl diglycol adipate and plasticizer TP-759.
Preferably, the modified multi-component filler is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fibers into the mixed acid, and carrying out ultrasonic treatment under heating; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of sulfuric acid and nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
2-2) adding the surface modified carbon fiber, the rare earth solution, the aluminum nitrate solution and the zinc acetate solution into acetone, and performing ultrasonic treatment to obtain a mixture, and performing ball milling;
2-3) stirring the product obtained in the step 2-2) for 5-10min, then dropwise adding ammonia water into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multielement filler by using functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, heating and stirring, centrifuging after the reaction is finished, washing a solid product, and drying in vacuum to obtain the modified multi-component filler.
Preferably, the modified multi-component filler is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fiber into mixed acid, and performing ultrasonic treatment at 60-80 deg.C for 2-4h; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum for 8-20h to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of 95 mass percent sulfuric acid and 65 mass percent nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
2-2) adding 1-5g of surface modified carbon fiber, rare earth solution, aluminum nitrate solution and zinc acetate solution into 200-500mL of acetone, and performing ultrasonic treatment for 15-30min to obtain a mixture, and performing ball milling for 0.5-4h;
2-3) stirring the product obtained in the step 2-2) for 5-10min, then dropwise adding ammonia water with the mass fraction of 5-15% into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 4-12h at 350-650 ℃ under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multielement filler by using functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment for 30-90min to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 0.5-3h at 45-70 ℃, standing for 3-8h, centrifuging, washing a solid product, and vacuum drying at 50-70 ℃ to obtain the modified multi-component filler.
Preferably, in the step 2-1), the mass ratio of the added cerium nitrate to the samarium nitrate is 3.
Preferably, in the step 2-2), the total mass of cerium and samarium in the added rare earth solution is 0.6-5% of the mass of the surface-modified carbon fiber, the mass ratio of the added aluminum ions to the surface-modified carbon fiber is 4-1 to 1, and the mass ratio of the added zinc ions to the surface-modified carbon fiber is 1.
Preferably, in the step 3), the added amount of the methylol urea is 1.5 to 5 times of the mass of the functionalized carbon fiber, and the added amount of the ammonium chloride is 4 to 10 percent of the mass of the functionalized carbon fiber.
The beneficial effects of the invention are:
the rubber compound prepared by the invention has excellent aging resistance and high elasticity, and the carbon fiber, the nano zinc oxide and the nano aluminum oxide are constructed into a composite system by virtue of rare earth elements to form the modified multi-element filler, so that the defects of easy agglomeration and poor compatibility with an organic system of the carbon fiber, the nano zinc oxide and the nano aluminum oxide can be overcome, and the comprehensive performance of the rubber compound can be greatly improved by the modified multi-element filler through the synergistic enhancement effect among materials.
Firstly, acidizing the carbon fiber, and introducing a large number of oxygen-containing active groups such as carboxyl, hydroxyl and the like on the surface of the carbon fiber; then, the rare earth elements (cerium and samarium) are connected to the surface of the carbon fiber by forming coordination bonds with a large number of oxygen-containing active groups through high chemical activity and strong coordination capacity of the rare earth elements;
meanwhile, aluminum ions and zinc ions in the system can be combined with oxygen-containing active groups through electrostatic interaction so as to be connected to the surface of the carbon fiber, and in the process, the rare earth elements can play a role in enhancing the combination of the aluminum ions and the zinc ions on the surface of the carbon fiber; then, calcining to enable rare earth cerium, rare earth samarium, aluminum ions and zinc ions to form stable oxides and firmly connect the stable oxides on the surface of the carbon fiber;
finally, by means of the bridging effect of rare earth elements, organic methylol urea is grafted on the surface of the carbon fiber, active groups containing oxygen and nitrogen are further introduced into the surface of the carbon fiber, and finally the modified multi-component filler with the surface chemical activity remarkably improved is obtained 2 ) Samarium oxide (Sm) 2 O 3 ) The aluminum oxide and the zinc oxide have comprehensive improvement effects on the aging resistance, elasticity and strength of the rubber compound.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are all conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The invention provides a preparation method of an aging-resistant high-elasticity rubber compound, which comprises the following steps:
s1, stirring and mixing a thermoplastic polyester elastomer, styrene butadiene rubber and ethylene acrylate rubber at 135-180 ℃ for 0.5-2h;
s2, after the product obtained in the step S1 is cooled to 50-70 ℃, transferring the product into an open mill, adding polytetrafluoroethylene, stearic acid and modified multi-element filler into the open mill, and mixing for 5-20min at 65-85 ℃;
s3, adding a vulcanizing agent and an auxiliary agent into the open mill, and mixing for 10-25min at 75-95 ℃ to obtain the aging-resistant high-elasticity rubber compound.
The raw materials for preparing the ageing-resistant high-elasticity rubber compound comprise the following components in parts by weight:
28-44 parts of thermoplastic polyester elastomer;
45-86 parts of styrene butadiene rubber;
30-62 parts of ethylene acrylate rubber;
4-18 parts of polytetrafluoroethylene;
2-6.5 parts of stearic acid;
18-46 parts of modified multi-component filler;
2-6 parts of a vulcanizing agent;
3.5 to 18 portions of auxiliary agent.
In a preferred embodiment, the auxiliary agents comprise a vulcanization accelerator, an anti-aging agent and a plasticizer, and the raw materials for preparing the aging-resistant high-elasticity rubber compound comprise the following components in parts by weight:
28-44 parts of thermoplastic polyester elastomer;
45-86 parts of styrene butadiene rubber;
30-62 parts of ethylene acrylate rubber;
4-18 parts of polytetrafluoroethylene;
2-6.5 parts by weight of stearic acid;
18-46 parts of modified multi-element filler;
2-6 parts of a vulcanizing agent;
0.5-4 parts by weight of a vulcanization accelerator;
1-4 parts of anti-aging agent;
2-10 parts of plasticizer.
In a preferred embodiment, the vulcanizing agent is bisphenol AF or vulcanizing agent DCP, the vulcanization accelerator is accelerator TMTD or accelerator TT, the anti-aging agent is one or a mixture of two of anti-aging agent 4010NA and anti-aging agent D, and the plasticizer is one or a mixture of more of dioctyl phthalate, dibutyl diglycol adipate and plasticizer TP-759.
In the invention, the modified multi-element filler is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fiber into mixed acid, and performing ultrasonic treatment at 60-80 deg.C for 2-4h; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum for 8-20h to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of 95 mass percent sulfuric acid and 65 mass percent nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
wherein the mass ratio of the added cerous nitrate to the samarium nitrate is 3.
2-2) adding 1-5g of surface modified carbon fiber, rare earth solution, aluminum nitrate solution and zinc acetate solution into 200-500mL of acetone, performing ultrasonic treatment for 15-30min, and performing ball milling on the obtained mixture for 0.5-4h;
wherein the total mass of cerium and samarium in the added rare earth solution is 0.6-5% of the mass of the surface modified carbon fiber, the mass ratio of the added aluminum ions to the surface modified carbon fiber is 4-1.
2-3) stirring the product obtained in the step 2-2) for 5-10min, then dropwise adding ammonia water with the mass fraction of 5-15% into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 4-12h at 350-650 ℃ under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multi-element filler by utilizing functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment for 30-90min to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 0.5-3h at 45-70 ℃, standing for 3-8h, centrifuging, washing a solid product, and vacuum drying at 50-70 ℃ to obtain a modified multi-component filler;
wherein the adding mass of the hydroxymethyl urea is 1.5-5 times of that of the functionalized carbon fiber, and the adding amount of the ammonium chloride is 4-10% of that of the functionalized carbon fiber.
Thermoplastic polyester elastomers (TPEEs) are block copolymers containing polyester hard segments and polyether soft segments. Wherein the soft polyether segment and the uncrystallized polyester form an amorphous phase, and the hard polyester segment is partially crystallized to form a crystalline micro-region which plays the role of a physical crosslinking point; the soft segments impart elasticity thereto and the hard segments impart processability thereto. According to the invention, TPEE is added, so that the elasticity of the rubber compound can be effectively improved. The ethylene acrylate rubber (AEM) is synthetic rubber consisting of ethylene and acrylic acid monomers, and the compounding of the AEM can improve the aging resistance of the rubber compound and further improve the elasticity. The addition of the polytetrafluoroethylene can effectively improve the strength and the aging resistance of the rubber compound.
The carbon fiber has the advantages of high strength, high modulus and the like, is an excellent filler used as a material reinforcing phase, and is widely applied to the preparation of various organic composite materials. The carbon fiber can form a net structure in the rubber compound, so that the strength and the toughness of a rubber compound system can be improved, and the resilience of the rubber compound is enhanced. However, carbon fiber has poor compatibility with organic matrix materials due to surface inertness and the like, has low interface bonding strength, is easy to agglomerate and tangle in the matrix materials, and makes the high performance of the carbon fiber difficult to be fully exerted, which also becomes an important defect affecting the corresponding application of the carbon fiber as reinforcement in organic composite materials.
The nano zinc oxide is a common additive in rubber compound, when the zinc oxide and the stearic acid are compounded, the zinc oxide and the stearic acid form zinc soap, and the zinc soap and a sulfur-containing rubber accelerator side hanging group are subjected to chelation reaction, so that a weak bond is in a stable state, the cracking position of a sulfur bond is changed, the rubber is vulcanized to generate a short cross-linking bond, a new cross-linking bond is added, the cross-linking density is improved, and the toughness of the rubber compound is enhanced; in addition, during vulcanization and use, the polysulfide bonds in the rubber are broken, producing H 2 S can accelerate rubber cracking, and zinc oxide can react with the rubber to form a new cross-linking bond, so that a vulcanized network is stabilized, and the aging resistance is improved; therefore, the zinc oxide can effectively improve the toughness and the aging resistance of the rubber. However, the nano zinc oxide has high surface activity, is easy to agglomerate and has poor compatibility with an organic system, so that the nano zinc oxide is difficult to fully disperse in a rubber mixing system and difficult to effectively exert the performance of the nano zinc oxide.
The nano alumina has high strength, high heat resistance and high stability, and can improve the hardness and weather resistance of the material when added into a rubber compound system; however, like nano zinc oxide, nano aluminum oxide also has the defects of easy agglomeration and difficulty in sufficient dispersion in a rubber compound system.
According to the invention, the carbon fiber, the nano zinc oxide and the nano aluminum oxide are constructed into a composite system by virtue of rare earth elements to form the modified multi-element filler, so that the defects of the carbon fiber, the nano zinc oxide and the nano aluminum oxide can be overcome to fully exert the performance of the carbon fiber, the nano zinc oxide and the nano aluminum oxide, and the comprehensive performance of the rubber compound can be greatly improved by the modified multi-element filler through the synergistic enhancement effect among the materials. The mechanism of the modified polyvalent filler will be described in detail below.
Firstly, acidizing the carbon fiber, and introducing a large number of oxygen-containing active groups such as carboxyl, hydroxyl and the like on the surface of the carbon fiber; then the rare earth elements (cerium and samarium) are connected to the surface of the carbon fiber by forming coordination bonds with a large number of oxygen-containing active groups through the high chemical activity and strong coordination capacity of the rare earth elements;
meanwhile, aluminum ions and zinc ions in the system can be combined with oxygen-containing active groups through electrostatic action so as to be connected to the surface of the carbon fiber, and in the process, the rare earth elements can play a role in enhancing the combination of the aluminum ions and the zinc ions on the surface of the carbon fiber; then, calcining to ensure that rare earth cerium, rare earth samarium, aluminum ions and zinc ions form stable oxides and are firmly connected to the surface of the carbon fiber;
finally, by means of the bridging effect of rare earth elements, organic hydroxymethyl urea is grafted on the surface of the carbon fiber, active groups containing oxygen and nitrogen are further introduced into the surface of the carbon fiber, and finally the modified multi-element filler with the surface chemical activity remarkably improved is obtained 2 ) Samarium oxide (Sm) 2 O 3 ) And the aluminum oxide and the zinc oxide have comprehensive improvement effects on the aging resistance, elasticity and strength of the rubber compound.
In the invention, in the constructed rare earth element-carbon fiber-zinc oxide-aluminum oxide composite structure system, carbon fibers can be mutually overlapped in a matrix to form a three-dimensional network structure, so that the strength and toughness of the matrix are enhanced; the zinc oxide and aluminum oxide particles grafted on the carbon fibers can become reinforced connection points of a three-dimensional network structure, so that the strength and the toughness of the network structure can be improved; on the other hand, the carbon fiber is used as a carrier, so that the zinc oxide and aluminum oxide particles are uniformly loaded on the surface of the carbon fiber, and the aggregation of the nano zinc oxide and nano aluminum oxide particles can be reduced, so that the uniform dispersion of the nano zinc oxide and nano aluminum oxide particles can be realized.
In the invention, the introduction of rare earth cerium and samarium into the carbon fiber-nano zirconia composite structure system can play at least the following roles:
(1) The rare earth element has high chemical activity, the internal electron layer contains a plurality of empty electron orbitals, the empty electron orbitals can be provided for molecules containing oxygen active groups to generate coordination bonds, and the rare earth cerium and samarium atoms have high proton number, so that the rare earth element has strong attraction to electrons and can effectively improve the content of active groups on the surface of the carbon fiber;
rare earth cerium and samarium can activate the surface of the carbon fiber, improve the quantity of oxygen-containing functional groups on the surface of the carbon fiber and improve the dispersion performance of the carbon fiber in an organic matrix, rare earth coordination bonds are formed among the cerium and samarium, the oxygen-containing functional groups and the organic matrix system, and the rare earth cerium and samarium are used as bridges to connect the carbon fiber and hydroxymethyl urea on the one hand and the carbon fiber and a rubber compound matrix on the other hand, so that the interface connection strength can be greatly improved, and the resilience and the strength of the material are improved;
(2) The rare earth cerium and samarium can be combined with oxygen-containing free radicals generated in the rubber aging process, and can quickly terminate the oxidation chain reaction in the rubber, effectively prevent the oxidation crosslinking of side chains, thereby improving the aging resistance of the rubber;
(3) The rare earth cerium and samarium have large and multiple coordination numbers, and can graft hydroxymethyl urea onto the surface of the carbon fiber (to form a mixed complex) through coordination after forming a complex with oxygen-containing functions on the surface of the carbon fiber, and the complex formed by the hydroxymethyl urea, the cerium and the samarium can form mechanical anchor points in an interface layer after being added into a rubber compound system, and the anchor points can play a role in enhancing the mechanical property;
according to the invention, the grafting of hydroxymethyl urea leads nitrogen-containing groups and more oxygen-containing groups to be introduced into the surface of carbon fiber, and the carbon fiber becomes groups with higher chemical activity under the action of rare earth cerium and samarium, and the chemical active groups can generate an interfacial chemical reaction with a rubber compound substrate to generate chemical bonds, so that on one hand, the compatibility of the carbon fiber and the substrate is further improved, the carbon fiber and the substrate can be fully and uniformly dispersed in the substrate, on the other hand, the bonding strength of the carbon fiber and the substrate interface can also be improved, and thus the overall mechanical performance of the rubber compound is improved.
The present invention is further illustrated by the following examples and comparative examples, which are given above as a general idea of the present invention. In the following examples, TPEE (thermoplastic polyester elastomer) is designated by Hytrel5556, styrene-butadiene rubber is designated by SBR1502, and ethylene acrylate rubber is designated by Vamac (R) G.
Example 1
The preparation method of the aging-resistant high-elasticity rubber compound comprises the following steps:
s1, stirring and mixing a thermoplastic polyester elastomer, styrene butadiene rubber and ethylene acrylate rubber at 160 ℃ for 1h;
s2, after the product obtained in the step S1 is cooled to 60 ℃, transferring the product into an open mill, adding polytetrafluoroethylene, stearic acid and modified multi-element filler into the open mill, and mixing for 15min at 75 ℃;
s3, adding a vulcanizing agent, a vulcanization accelerator, an anti-aging agent and a plasticizer into the open mill, and mixing for 20min at 80 ℃ to obtain an anti-aging high-elasticity rubber compound;
the raw materials for preparing the ageing-resistant high-elasticity rubber compound comprise the following components in parts by weight:
33 parts by weight of a thermoplastic polyester elastomer;
72 parts of styrene butadiene rubber;
45 parts by weight of ethylene acrylate rubber;
11 parts of polytetrafluoroethylene;
4.5 parts by weight of stearic acid;
34 parts of modified multi-component filler;
3.8 parts by weight of a vulcanizing agent;
2.5 parts by weight of a vulcanization accelerator;
2 parts of anti-aging agent;
6 parts of a plasticizer.
Wherein the vulcanizing agent is bisphenol AF, the vulcanization accelerator is accelerator TMTDTT, the anti-aging agent is a mixture of anti-aging agent 4010NA and anti-aging agent D, and the plasticizer is plasticizer TP-759.
In the invention, the modified multi-element filler is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fibers into mixed acid, and performing ultrasonic treatment for 3 hours at 70 ℃; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum for 12h to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of 95 mass percent sulfuric acid and 65 mass percent nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
wherein the mass ratio of the added cerium nitrate to the samarium nitrate is 3.
2-2) adding 2g of surface modified carbon fiber, a rare earth solution, an aluminum nitrate solution and a zinc acetate solution into 400mL of acetone, and performing ultrasonic treatment for 25min to obtain a mixture, and performing ball milling for 2h;
wherein the total mass of cerium and samarium in the added rare earth solution is 1.2% of the mass of the surface modified carbon fiber, the mass ratio of the added aluminum ions to the surface modified carbon fiber is 2.
2-3) stirring the product obtained in the step 2-2) for 5min, then dropwise adding ammonia water with the mass fraction of 10% into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 8h at 580 ℃ under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multielement filler by using functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment for 40min to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 2h at 55 ℃, standing for 6h, centrifuging, washing a solid product, and drying in vacuum at 50 ℃ to obtain a modified multi-element filler;
wherein the addition amount of the hydroxymethyl urea is 2.5 times of the mass of the functionalized carbon fiber, and the addition amount of the ammonium chloride is 5 percent of the mass of the functionalized carbon fiber.
Example 2
The preparation method of the aging-resistant high-elasticity rubber compound comprises the following steps:
s1, stirring and mixing a thermoplastic polyester elastomer, styrene butadiene rubber and ethylene acrylate rubber at 160 ℃ for 1h;
s2, after the product obtained in the step S1 is cooled to 60 ℃, transferring the product into an open mill, adding polytetrafluoroethylene, stearic acid and modified multi-element filler into the open mill, and mixing for 15min at 75 ℃;
s3, adding a vulcanizing agent, a vulcanization accelerator, an anti-aging agent and a plasticizer into the open mill, and mixing for 20min at 80 ℃ to obtain an anti-aging high-elasticity rubber compound;
the raw materials for preparing the ageing-resistant high-elasticity rubber compound comprise the following components in parts by weight:
33 parts by weight of a thermoplastic polyester elastomer;
72 parts of styrene butadiene rubber;
45 parts by weight of ethylene acrylate rubber;
11 parts of polytetrafluoroethylene;
4.5 parts by weight of stearic acid;
30 parts of modified multi-component filler;
3.8 parts by weight of a vulcanizing agent;
2.5 parts by weight of a vulcanization accelerator;
2 parts of anti-aging agent;
6 parts of a plasticizer.
Wherein, the vulcanizing agent is bisphenol AF, the vulcanization accelerator is TMTDTT, the anti-aging agent is a mixture of anti-aging agent 4010NA and anti-aging agent D, and the plasticizer is plasticizer TP-759.
In the invention, the modified multi-element filler is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fibers into mixed acid, and performing ultrasonic treatment for 3 hours at 70 ℃; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum for 12h to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of 95 mass percent sulfuric acid and 65 mass percent nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
wherein the mass ratio of the added cerium nitrate to the samarium nitrate is 3.
2-2) adding 2g of surface modified carbon fiber, a rare earth solution, an aluminum nitrate solution and a zinc acetate solution into 400mL of acetone, and performing ultrasonic treatment for 25min to obtain a mixture, and performing ball milling for 2h;
wherein the total mass of cerium and samarium in the added rare earth solution is 1.2% of the mass of the surface modified carbon fiber, the mass ratio of the added aluminum ions to the surface modified carbon fiber is 2.
2-3) stirring the product obtained in the step 2-2) for 5min, then dropwise adding ammonia water with the mass fraction of 10% into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 8h at 580 ℃ under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multi-element filler by utilizing functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment for 40min to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 2h at 55 ℃, standing for 6h, centrifuging, washing a solid product, and drying in vacuum at 50 ℃ to obtain a modified multi-component filler;
wherein the addition amount of the hydroxymethyl urea is 2.5 times of the mass of the functionalized carbon fiber, and the addition amount of the ammonium chloride is 5 percent of the mass of the functionalized carbon fiber.
Example 3
The preparation method of the aging-resistant high-elasticity rubber compound comprises the following steps:
s1, stirring and mixing a thermoplastic polyester elastomer, styrene butadiene rubber and ethylene acrylate rubber at 160 ℃ for 1h;
s2, after the product obtained in the step S1 is cooled to 60 ℃, transferring the product into an open mill, adding polytetrafluoroethylene, stearic acid and modified multi-element filler into the open mill, and mixing for 15min at 75 ℃;
s3, adding a vulcanizing agent, a vulcanization accelerator, an anti-aging agent and a plasticizer into the open mill, and mixing for 20min at 80 ℃ to obtain an anti-aging high-elasticity rubber compound;
the raw materials for preparing the ageing-resistant high-elasticity rubber compound comprise the following components in parts by weight:
33 parts by weight of a thermoplastic polyester elastomer;
72 parts of styrene butadiene rubber;
45 parts of ethylene acrylate rubber;
11 parts of polytetrafluoroethylene;
4.5 parts by weight of stearic acid;
38 parts of modified multi-component filler;
3.8 parts by weight of a vulcanizing agent;
2.5 parts by weight of a vulcanization accelerator;
2 parts of anti-aging agent;
6 parts of a plasticizer.
Wherein the vulcanizing agent is bisphenol AF, the vulcanization accelerator is accelerator TMTDTT, the anti-aging agent is a mixture of anti-aging agent 4010NA and anti-aging agent D, and the plasticizer is plasticizer TP-759.
In the invention, the modified multi-element filler is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fiber into mixed acid, and performing ultrasonic treatment for 3h at 70 ℃; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum for 12h to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of 95 mass percent sulfuric acid and 65 mass percent nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
wherein the mass ratio of the added cerium nitrate to the samarium nitrate is 3.
2-2) adding 2g of surface modified carbon fiber, a rare earth solution, an aluminum nitrate solution and a zinc acetate solution into 400mL of acetone, and performing ultrasonic treatment for 25min to obtain a mixture, and performing ball milling for 2h;
wherein the total mass of cerium and samarium in the added rare earth solution is 1.2% of the mass of the surface modified carbon fiber, the mass ratio of the added aluminum ions to the surface modified carbon fiber is 2.
2-3) stirring the product obtained in the step 2-2) for 5min, then dropwise adding ammonia water with the mass fraction of 10% into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 8h at 580 ℃ under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multi-element filler by utilizing functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment for 40min to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 2h at 55 ℃, standing for 6h, centrifuging, washing a solid product, and drying in vacuum at 50 ℃ to obtain a modified multi-element filler;
wherein the adding mass of the hydroxymethyl urea is 2.5 times of that of the functionalized carbon fiber, and the adding amount of the ammonium chloride is 5 percent of that of the functionalized carbon fiber.
Example 4
A preparation method of an aging-resistant high-elasticity rubber compound comprises the following steps:
s1, stirring and mixing a thermoplastic polyester elastomer, styrene butadiene rubber and ethylene acrylate rubber at 160 ℃ for 1h;
s2, after the product obtained in the step S1 is cooled to 60 ℃, transferring the product into an open mill, adding polytetrafluoroethylene, stearic acid and modified multi-element filler into the open mill, and mixing for 15min at 75 ℃;
s3, adding a vulcanizing agent, a vulcanization accelerator, an anti-aging agent and a plasticizer into the open mill, and mixing for 20min at 80 ℃ to obtain an anti-aging high-elasticity rubber compound;
the raw materials for preparing the ageing-resistant high-elasticity rubber compound comprise the following components in parts by weight:
33 parts by weight of a thermoplastic polyester elastomer;
72 parts of styrene butadiene rubber;
45 parts by weight of ethylene acrylate rubber;
11 parts of polytetrafluoroethylene;
4.5 parts by weight of stearic acid;
34 parts of modified multi-component filler;
3.8 parts by weight of a vulcanizing agent;
2.5 parts by weight of a vulcanization accelerator;
2 parts of anti-aging agent;
6 parts of a plasticizer.
Wherein the vulcanizing agent is bisphenol AF, the vulcanization accelerator is accelerator TMTDTT, the anti-aging agent is a mixture of anti-aging agent 4010NA and anti-aging agent D, and the plasticizer is plasticizer TP-759.
In the invention, the modified multi-element filler is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fiber into mixed acid, and performing ultrasonic treatment for 3h at 70 ℃; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum for 12h to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of 95 mass percent sulfuric acid and 65 mass percent nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
wherein the mass ratio of the added cerium nitrate to the samarium nitrate is 3.
2-2) adding 2g of surface modified carbon fiber, a rare earth solution, an aluminum nitrate solution and a zinc acetate solution into 400mL of acetone, and performing ultrasonic treatment for 25min to obtain a mixture, and performing ball milling for 2h;
wherein the total mass of cerium and samarium in the added rare earth solution is 1.5% of the mass of the surface modified carbon fiber, the mass ratio of the added aluminum ions to the surface modified carbon fiber is 2.
2-3) stirring the product obtained in the step 2-2) for 5min, then dropwise adding 10% ammonia water into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 8h at 580 ℃ under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multi-element filler by utilizing functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment for 40min to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 2h at 55 ℃, standing for 6h, centrifuging, washing a solid product, and drying in vacuum at 50 ℃ to obtain a modified multi-component filler;
wherein the addition amount of the hydroxymethyl urea is 2.5 times of the mass of the functionalized carbon fiber, and the addition amount of the ammonium chloride is 5 percent of the mass of the functionalized carbon fiber.
Example 5
A preparation method of an aging-resistant high-elasticity rubber compound comprises the following steps:
s1, stirring and mixing a thermoplastic polyester elastomer, styrene butadiene rubber and ethylene acrylate rubber at 160 ℃ for 1h;
s2, after the product obtained in the step S1 is cooled to 60 ℃, transferring the product into an open mill, adding polytetrafluoroethylene, stearic acid and modified multi-element filler into the open mill, and mixing for 15min at 75 ℃;
s3, adding a vulcanizing agent, a vulcanization accelerator, an anti-aging agent and a plasticizer into the open mill, and mixing for 20min at 80 ℃ to obtain an anti-aging high-elasticity rubber compound;
the raw materials for preparing the ageing-resistant high-elasticity rubber compound comprise the following components in parts by weight:
33 parts by weight of thermoplastic polyester elastomer;
72 parts of styrene butadiene rubber;
45 parts by weight of ethylene acrylate rubber;
11 parts of polytetrafluoroethylene;
4.5 parts by weight of stearic acid;
34 parts of modified multi-component filler;
3.8 parts by weight of a vulcanizing agent;
2.5 parts by weight of a vulcanization accelerator;
2 parts of anti-aging agent;
6 parts of a plasticizer.
Wherein, the vulcanizing agent is bisphenol AF, the vulcanization accelerator is TMTDTT, the anti-aging agent is a mixture of anti-aging agent 4010NA and anti-aging agent D, and the plasticizer is plasticizer TP-759.
In the invention, the modified multi-element filler is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fibers into mixed acid, and performing ultrasonic treatment for 3 hours at 70 ℃; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum for 12h to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of 95 mass percent sulfuric acid and 65 mass percent nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
wherein the mass ratio of the added cerium nitrate to the samarium nitrate is 3.
2-2) adding 2g of surface modified carbon fiber, a rare earth solution, an aluminum nitrate solution and a zinc acetate solution into 400mL of acetone, and performing ultrasonic treatment for 25min to obtain a mixture, and performing ball milling for 2h;
wherein the total mass of cerium and samarium in the added rare earth solution is 1.8% of the mass of the surface modified carbon fiber, the mass ratio of the added aluminum ions to the surface modified carbon fiber is 2.
2-3) stirring the product obtained in the step 2-2) for 5min, then dropwise adding ammonia water with the mass fraction of 10% into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 8h at 580 ℃ under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multi-element filler by utilizing functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment for 40min to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 2h at 55 ℃, standing for 6h, centrifuging, washing a solid product, and drying in vacuum at 50 ℃ to obtain a modified multi-component filler;
wherein the addition amount of the hydroxymethyl urea is 2.5 times of the mass of the functionalized carbon fiber, and the addition amount of the ammonium chloride is 5 percent of the mass of the functionalized carbon fiber.
Comparative example 1
A method for preparing a rubber compound comprises the following steps:
s1, stirring and mixing a thermoplastic polyester elastomer, styrene butadiene rubber and ethylene acrylate rubber at 160 ℃ for 1h;
s2, after the product obtained in the step S1 is cooled to 60 ℃, transferring the product into an open mill, adding polytetrafluoroethylene, stearic acid, carbon fiber, nano aluminum oxide, nano zinc oxide, cerium oxide and samarium oxide into the open mill, and mixing for 15min at 75 ℃;
s3, adding a vulcanizing agent, a vulcanization accelerator, an anti-aging agent and a plasticizer into the open mill, and mixing for 20min at 80 ℃ to obtain a rubber compound;
the raw materials for preparing the rubber compound comprise the following components in parts by weight:
33 parts by weight of thermoplastic polyester elastomer;
72 parts of styrene butadiene rubber;
45 parts by weight of ethylene acrylate rubber;
11 parts of polytetrafluoroethylene;
4.5 parts by weight of stearic acid;
20 parts by weight of carbon fibers;
9 parts of nano alumina;
4 parts of nano zinc oxide;
0.6 part by weight of cerium oxide;
0.4 part by weight of samarium oxide;
34 parts of modified multi-element filler;
3.8 parts by weight of a vulcanizing agent;
2.5 parts by weight of a vulcanization accelerator;
2 parts of anti-aging agent;
6 parts of a plasticizer.
Wherein, the vulcanizing agent is bisphenol AF, the vulcanization accelerator is TMTDTT, the anti-aging agent is a mixture of anti-aging agent 4010NA and anti-aging agent D, and the plasticizer is plasticizer TP-759.
Comparative example 2
This example is substantially the same as example 1, except that:
the modified multi-component filler in the example is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fiber into mixed acid, and performing ultrasonic treatment for 3h at 70 ℃; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum for 12h to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of 95 mass percent sulfuric acid and 65 mass percent nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1;
2) Preparing a functional carbon fiber filler:
2-1) adding 2g of surface modified carbon fiber, an aluminum nitrate solution and a zinc acetate solution into 400mL of acetone, and performing ultrasonic treatment for 25min to obtain a mixture, and performing ball milling for 2h;
the mass ratio of the added aluminum ions to the surface-modified carbon fibers is 2.
2-3) stirring the product obtained in the step 2-2) for 5min, then dropwise adding ammonia water with the mass fraction of 10% into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 8h at 580 ℃ under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multielement filler by using functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment for 40min to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 2h at 55 ℃, standing for 6h, centrifuging, washing a solid product, and drying in vacuum at 50 ℃ to obtain a modified multi-component filler;
wherein the adding mass of the hydroxymethyl urea is 2.5 times of that of the functionalized carbon fiber, and the adding amount of the ammonium chloride is 5 percent of that of the functionalized carbon fiber.
Comparative example 3
This example is substantially the same as example 1, except that:
the modified multi-component filler in the example is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fibers into mixed acid, and performing ultrasonic treatment for 3 hours at 70 ℃; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum for 12h to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of 95 mass percent sulfuric acid and 65 mass percent nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
wherein the mass ratio of the added cerium nitrate to the samarium nitrate is 3.
2-2) adding 2g of surface modified carbon fiber, rare earth solution and zinc acetate solution into 400mL of acetone, and performing ultrasonic treatment for 25min to obtain a mixture, and performing ball milling for 2h;
wherein the total mass of cerium and samarium in the added rare earth solution is 1.2% of the mass of the surface modified carbon fiber, and the mass ratio of the added zinc ions to the surface modified carbon fiber is 1.
2-3) stirring the product obtained in the step 2-2) for 5min, then dropwise adding ammonia water with the mass fraction of 10% into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 8h at 580 ℃ under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multi-element filler by utilizing functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment for 40min to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 2h at 55 ℃, standing for 6h, centrifuging, washing a solid product, and drying in vacuum at 50 ℃ to obtain a modified multi-component filler;
wherein the adding mass of the hydroxymethyl urea is 2.5 times of that of the functionalized carbon fiber, and the adding amount of the ammonium chloride is 5 percent of that of the functionalized carbon fiber.
Comparative example 4
This example is substantially the same as example 1, except that:
the modified multi-component filler in the example is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fibers into mixed acid, and performing ultrasonic treatment for 3 hours at 70 ℃; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum for 12h to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of 95 mass percent sulfuric acid and 65 mass percent nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
wherein the mass ratio of the added cerium nitrate to the samarium nitrate is 3.
2-2) adding 2g of surface modified carbon fiber, a rare earth solution, an aluminum nitrate solution and a zinc acetate solution into 400mL of acetone, and performing ultrasonic treatment for 25min to obtain a mixture, and performing ball milling for 2h;
wherein the total mass of cerium and samarium in the added rare earth solution is 1.2% of the mass of the surface modified carbon fiber, the mass ratio of the added aluminum ions to the surface modified carbon fiber is 2.
2-3) stirring the product obtained in the step 2-2) for 5min, then dropwise adding 10% ammonia water into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 8h at 580 ℃ under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler, wherein the functionalized carbon fiber filler is used as the modified multi-element filler.
Comparative example 5
A method for preparing a rubber compound comprises the following steps:
s1, stirring and mixing a thermoplastic polyester elastomer, styrene butadiene rubber and ethylene acrylate rubber at 160 ℃ for 1h;
s2, after the product obtained in the step S1 is cooled to 60 ℃, transferring the product into an open mill, adding polytetrafluoroethylene, stearic acid, nano zinc oxide and modified multi-element filler into the open mill, and mixing for 15min at 75 ℃;
s3, adding a vulcanizing agent, a vulcanization accelerator, an anti-aging agent and a plasticizer into the open mill, and mixing for 20min at 80 ℃ to obtain a rubber compound;
the raw materials for preparing the rubber compound comprise the following components in parts by weight:
33 parts by weight of a thermoplastic polyester elastomer;
72 parts of styrene butadiene rubber;
45 parts of ethylene acrylate rubber;
11 parts of polytetrafluoroethylene;
4.5 parts by weight of stearic acid;
4 parts of nano zinc oxide;
34 parts of modified multi-element filler;
3.8 parts by weight of a vulcanizing agent;
2.5 parts by weight of a vulcanization accelerator;
2 parts of anti-aging agent;
6 parts of a plasticizer.
Wherein, the vulcanizing agent is bisphenol AF, the vulcanization accelerator is TMTDTT, the anti-aging agent is a mixture of anti-aging agent 4010NA and anti-aging agent D, and the plasticizer is plasticizer TP-759.
In the invention, the modified multi-element filler is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fiber into mixed acid, and performing ultrasonic treatment for 3h at 70 ℃; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum for 12 hours to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of 95 mass percent sulfuric acid and 65 mass percent nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
wherein the mass ratio of the added cerium nitrate to the samarium nitrate is 3.
2-2) adding 2g of surface modified carbon fiber, rare earth solution and aluminum nitrate solution into 400mL of acetone, and performing ultrasonic treatment for 25min to obtain a mixture, and performing ball milling for 2h;
wherein the total mass of cerium and samarium in the added rare earth solution is 1.2% of the mass of the surface modified carbon fiber, and the mass ratio of the added aluminum ions to the surface modified carbon fiber is 2.
2-3) stirring the product obtained in the step 2-2) for 5min, then dropwise adding ammonia water with the mass fraction of 10% into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 8h at 580 ℃ under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multielement filler by using functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment for 40min to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 2h at 55 ℃, standing for 6h, centrifuging, washing a solid product, and drying in vacuum at 50 ℃ to obtain a modified multi-component filler;
wherein the adding mass of the hydroxymethyl urea is 2.5 times of that of the functionalized carbon fiber, and the adding amount of the ammonium chloride is 5 percent of that of the functionalized carbon fiber.
The mixes obtained in examples 1 to 4 and comparative examples 1 to 4 were vulcanized: and (3) carrying out primary vulcanization at 165 ℃ for 15min and secondary vulcanization at 200 ℃ for 4h to obtain vulcanized rubber, and carrying out performance detection on the vulcanized rubber, wherein the detection items comprise:
compression set property: testing is carried out according to the standard GB/T7759-2015;
tensile property: testing with reference to standard GB-T528-2009;
shore A hardness: testing according to the standard GB-T531.1-2008;
heat aging performance: the test is carried out according to the standard GB/T3512-2014, and the hot air aging condition is 220 ℃ multiplied by 72h.
The results are shown in tables 1 and 2 below:
TABLE 1
TABLE 2
As can be seen from the test results in tables 1 and 2, the rubber mixtures prepared in examples 1 to 5 of the present invention have excellent aging resistance and high elasticity; in comparative example 1, additives such as carbon fiber, nano aluminum oxide, nano zinc oxide, cerium oxide, samarium oxide and the like are added in a monomer form, and because the monomers are difficult to be fully dispersed in a rubber compound system, the comprehensive performance of the obtained rubber compound is remarkably reduced; the modified multi-element filler in the comparative example 2 lacks rare earth cerium and samarium, and the performance of rubber compound is obviously reduced; no methylol-free urea is introduced into the modified multi-element filler of the comparative example 4, so that the compatibility of the modified multi-element filler and a rubber compound system is reduced, and the aging resistance and the elasticity of the rubber compound are reduced; the nano zinc oxide in comparative example 5, added in the form of a monomer, decreased in dispersibility in the rubber compound system, resulting in failure to sufficiently exert its properties, as manifested by a decrease in elasticity and strength.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (10)
1. The preparation method of the aging-resistant high-elasticity rubber compound is characterized by comprising the following steps of:
s1, stirring and mixing a thermoplastic polyester elastomer, styrene butadiene rubber and ethylene acrylate rubber at 135-180 ℃ for 0.5-2h;
s2, after the product obtained in the step S1 is cooled to 50-70 ℃, transferring the product into an open mill, adding polytetrafluoroethylene, stearic acid and modified multi-element filler into the open mill, and mixing for 5-20min at 65-85 ℃;
s3, adding a vulcanizing agent and an auxiliary agent into the open mill, and mixing for 10-25min at 75-95 ℃ to obtain the ageing-resistant high-elasticity rubber compound.
2. The method for preparing the aging-resistant high-elasticity rubber compound as claimed in claim 1, wherein the aging-resistant high-elasticity rubber compound is prepared from the following raw materials in parts by weight:
28-44 parts of thermoplastic polyester elastomer;
45-86 parts of styrene butadiene rubber;
30-62 parts of ethylene acrylate rubber;
4-18 parts of polytetrafluoroethylene;
2-6.5 parts of stearic acid;
18-46 parts of modified multi-element filler;
2-6 parts of a vulcanizing agent;
3.5 to 18 portions of auxiliary agent.
3. A method of producing a weatherable, highly elastic mix as claimed in claim 2, wherein said auxiliaries include a vulcanization accelerator, an anti-aging agent and a plasticizer.
4. The preparation method of the aging-resistant high-elasticity rubber compound as claimed in claim 3, wherein the raw materials for preparing the aging-resistant high-elasticity rubber compound comprise, by weight:
28-44 parts of thermoplastic polyester elastomer;
45-86 parts of styrene butadiene rubber;
30-62 parts of ethylene acrylate rubber;
4-18 parts of polytetrafluoroethylene;
2-6.5 parts of stearic acid;
18-46 parts of modified multi-element filler;
2-6 parts of a vulcanizing agent;
0.5-4 parts by weight of a vulcanization accelerator;
1-4 parts of anti-aging agent;
2-10 parts of plasticizer.
5. The method for preparing the aging-resistant high-elasticity rubber compound according to claim 4, wherein the vulcanizing agent is bisphenol AF or DCP, the vulcanization accelerator is TMTD or TT, the anti-aging agent is one or a mixture of two of anti-aging agent 4010NA and anti-aging agent D, and the plasticizer is one or a mixture of more of dioctyl phthalate, dibutyl diglycol adipate and plasticizer TP-759.
6. A method for preparing a high-elasticity ageing-resistant rubber compound according to any one of claims 1 to 5, wherein the modified multi-component filler is prepared by:
1) Preparing surface modified carbon fiber:
adding carbon fibers into the mixed acid, and carrying out ultrasonic treatment under heating; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of sulfuric acid and nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
2-2) adding the surface modified carbon fiber, the rare earth solution, the aluminum nitrate solution and the zinc acetate solution into acetone, and performing ultrasonic treatment to obtain a mixture, and performing ball milling;
2-3) stirring the product obtained in the step 2-2) for 5-10min, then dropwise adding ammonia water into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multielement filler by using functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, heating and stirring, centrifuging after the reaction is finished, washing a solid product, and drying in vacuum to obtain the modified multi-component filler.
7. A method for preparing a high elasticity rubber compound with aging resistance according to any one of claim 6, wherein the modified multi-element filler is prepared by the following method:
1) Preparing surface modified carbon fiber:
adding carbon fiber into mixed acid, and performing ultrasonic treatment at 60-80 deg.C for 2-4h; filtering, washing the solid product with deionized water to be neutral, and drying in vacuum for 8-20h to obtain surface modified carbon fiber;
wherein the mixed acid is a mixture of 95 mass percent sulfuric acid and 65 mass percent nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1;
2) Preparing a functional carbon fiber filler:
2-1) adding a mixture of cerium nitrate and samarium nitrate into ethanol to prepare a rare earth solution;
2-2) adding 1-5g of surface modified carbon fiber, rare earth solution, aluminum nitrate solution and zinc acetate solution into 200-500mL of acetone, and performing ultrasonic treatment for 15-30min to obtain a mixture, and performing ball milling for 0.5-4h;
2-3) stirring the product obtained in the step 2-2) for 5-10min, then dropwise adding ammonia water with the mass fraction of 5-15% into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 4-12h at 350-650 ℃ under the protection of argon, cooling, and grinding to obtain the functionalized carbon fiber filler;
3) Preparing modified multielement filler by using functionalized carbon fiber:
3-1) adding the functionalized carbon fiber filler into ethanol, and performing ultrasonic treatment for 30-90min to obtain a solution A;
3-2) adding ammonium chloride and hydroxymethyl urea into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 0.5-3h at 45-70 ℃, standing for 3-8h, centrifuging, washing a solid product, and vacuum drying at 50-70 ℃ to obtain the modified multi-component filler.
8. The method for preparing the aging-resistant high-elasticity rubber compound according to any one of claim 7, wherein in the step 2-1), the mass ratio of the added cerium nitrate to the samarium nitrate is 3.
9. The method for preparing the aging-resistant high-elasticity rubber compound according to any one of the claims 7, wherein in the step 2-2), the total mass of cerium and samarium in the rare earth solution is 0.6-5% of the mass of the surface-modified carbon fiber, the mass ratio of the added aluminum ions to the surface-modified carbon fiber is (4-1).
10. The method for preparing a high elasticity aging-resistant rubber compound as claimed in claim 7, wherein in step 3), the amount of methylol urea added is 1.5-5 times the amount of functionalized carbon fiber and the amount of ammonium chloride added is 4-10% of the amount of functionalized carbon fiber.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004043786A (en) * | 2002-05-16 | 2004-02-12 | Bridgestone Corp | Rubber composition |
| JP2009263456A (en) * | 2008-04-23 | 2009-11-12 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| CN105590754A (en) * | 2016-02-27 | 2016-05-18 | 北京化工大学 | Production method of multi-element transition metal hydroxide nuclear shell composite carbon filter electrode material |
| CN105602041A (en) * | 2016-01-28 | 2016-05-25 | 青岛科技大学 | High-hardness and high-elasticity NBR/TPEE blend rubber and preparing method |
| CN105968444A (en) * | 2016-07-25 | 2016-09-28 | 铜陵宏正网络科技有限公司 | Coating rubber material for toughened printing rubber rolls and preparation method of coating rubber material |
-
2022
- 2022-10-26 CN CN202211317736.2A patent/CN115627018A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004043786A (en) * | 2002-05-16 | 2004-02-12 | Bridgestone Corp | Rubber composition |
| JP2009263456A (en) * | 2008-04-23 | 2009-11-12 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| CN105602041A (en) * | 2016-01-28 | 2016-05-25 | 青岛科技大学 | High-hardness and high-elasticity NBR/TPEE blend rubber and preparing method |
| CN105590754A (en) * | 2016-02-27 | 2016-05-18 | 北京化工大学 | Production method of multi-element transition metal hydroxide nuclear shell composite carbon filter electrode material |
| CN105968444A (en) * | 2016-07-25 | 2016-09-28 | 铜陵宏正网络科技有限公司 | Coating rubber material for toughened printing rubber rolls and preparation method of coating rubber material |
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