CN115627017A - Ultra-high-hardness wear-resistant rubber compound - Google Patents
Ultra-high-hardness wear-resistant rubber compound Download PDFInfo
- Publication number
- CN115627017A CN115627017A CN202211317052.2A CN202211317052A CN115627017A CN 115627017 A CN115627017 A CN 115627017A CN 202211317052 A CN202211317052 A CN 202211317052A CN 115627017 A CN115627017 A CN 115627017A
- Authority
- CN
- China
- Prior art keywords
- parts
- carbon fiber
- ultra
- cnf
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an ultra-hard wear-resistant rubber compound which is prepared from the following raw materials in parts by weight: 60-92 parts of styrene butadiene rubber; 43-75 parts of butadiene rubber; 8-24 parts of polyether-ether-ketone; 22-46 parts of composite modified reinforcing agent; 1.5-4 parts by weight of stearic acid; 2-8.5 parts of zinc oxide; 3-6 parts of a plasticizer; 1.2-3 parts of anti-aging agent; 1.6-5 parts by weight of a vulcanizing agent; 0.5 to 3 weight portions of accelerant. According to the invention, the composite modified reinforcing agent is formed by constructing the carbon fiber, the nano zirconia, the rare earth element and the organic matter, and is used as the reinforcing filler to be added into the rubber compound matrix, so that the hardness and the wear resistance of the rubber compound can be greatly improved.
Description
Technical Field
The invention relates to the field of rubber materials, in particular to an ultra-hard wear-resistant rubber compound.
Background
The rubber compound can be widely used in the industries of aviation, cables, electronics, electrical appliances, chemical engineering, instruments, cement, automobiles, buildings, food processing, medical appliances and the like. In many application scenarios, high requirements are put on performances such as abrasion resistance and hardness of rubber compound, such as tires, conveyor belts, sealing elements and the like. The performance of a single rubber material is limited, and other materials are often required to be added for reinforcement so as to improve the comprehensive performance 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 can be applied to rubber compound to improve the wear resistance and hardness of the rubber compound; the nano zirconia has high strength and high stability, and is usually used as a reinforcing phase to improve the wear resistance, hardness and the like of materials based on excellent mechanical properties of the nano zirconia. For example, a super wear-resistant fluororubber compound disclosed in patent CN109517304B, a high-strength silicone rubber compound disclosed in patent CN105086456A, a preparation method thereof and the like.
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, entangle and the like in the matrix materials, so that the high performance of the carbon fiber is difficult to fully exert, and the carbon fiber is an important defect influencing the application of the carbon fiber in organic composite materials as reinforcement. Similarly, the nano zirconia has similar problems when used in an organic matrix material, and has a nano size, a large specific surface area, poor compatibility with an organic system and easy agglomeration, so that the nano zirconia is difficult to uniformly disperse in the organic system to fully exert the reinforcing performance of the nano zirconia.
Therefore, there is a need for improvements in the art to provide a more reliable solution.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a solution to the above-mentioned deficiencies in the prior art.
In order to solve the technical problems, the invention adopts the technical scheme that: an ultra-hard wear-resistant rubber compound is prepared from the following raw materials in parts by weight:
60-92 parts of styrene butadiene rubber;
43-75 parts of butadiene rubber;
8-24 parts of polyether-ether-ketone;
22-46 parts of composite modified reinforcing agent;
1.5-4 parts of stearic acid;
2-8.5 parts of zinc oxide;
3-6 parts of a plasticizer;
1.2-3 parts of anti-aging agent;
1.6-5 parts by weight of a vulcanizing agent;
0.5 to 3 weight portions of accelerant.
Preferably, the composite modified reinforcing agent is prepared by the following method:
1) Preparing acidified carbon fiber CNF;
2) Preparation of rare earth-modified carbon fiber-zirconia composite ZrO 2 @CNF-RE；
3) Using ZrO 2 The @ CNF-RE is mixed with ammonium chloride and 1, 3-bis (hydroxymethyl) imidazolidine-2-thione to prepare the composite modified reinforcing agent.
Preferably, the step 1) is specifically: 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 neutrality, and vacuum drying for 8-20h to obtain the acidified carbon fiber CNF.
Preferably, the mixed acid is a mixture of 95% by mass of sulfuric acid and 65% by mass of nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3:1.
preferably, the step 2) specifically includes:
2-1) adding a rare earth compound into ethanol to prepare a rare earth additive solution with the mass concentration of 0.05-1.2%;
2-2) adding 0.5-4g of acidified carbon fibers, a rare earth additive solution and an organic zirconium salt 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;
wherein, the mass of the rare earth is 0.5-4.5% of that of the acidified carbon fiber;
2-3) stirring the product obtained in the step 2) for 5-30min, then heating to 65-85 ℃, dropwise adding a sodium hydroxide solution with the temperature of 65-85 ℃ into the product under continuous stirring until the precipitate in a reaction system is not increased any moreStopping dropwise adding, filtering, washing the solid product to be neutral, sintering for 2-6h at 450-750 ℃ under the protection of argon, cooling and grinding to obtain the carbon fiber-zirconium oxide compound ZrO 2 @CNF-RE。
Preferably, the mass ratio of the zirconium ions added in the step 2-2) to the acidified carbon fibers is 5.
Preferably, the rare earth compound is a mixture of lanthanum chloride and yttrium chloride, and the mass ratio of lanthanum chloride to yttrium chloride is 2.
Preferably, the step 3) specifically includes:
3-1) ZrO treatment 2 Adding @ CNF-RE into ethanol, and performing ultrasonic treatment for 20-60min to obtain solution A;
3-2) adding ammonium chloride and 1, 3-bis (hydroxymethyl) imidazolidine-2-thione into ethanol, and stirring to obtain a solution B;
3-3) adding the solution B into the solution A, stirring for 0.5-2h at 40-60 ℃, standing for 2-6h, centrifuging, washing a solid product, and vacuum drying at 45-65 ℃ to obtain a composite modified reinforcing agent;
wherein, the added mass of the 1, 3-bis (hydroxymethyl) imidazolidine-2-thione is ZrO 2 1-4 times of @ CNF-RE, and the addition amount of ammonium chloride is ZrO 2 @ CNF-RE 5-8% by mass.
Preferably, the ultra-hard wear-resistant rubber compound is prepared by the following method:
s1, weighing raw materials according to the weight part ratio;
s2, adding polyether-ether-ketone, a composite modified reinforcing agent, stearic acid and zinc oxide into a mixer, and stirring for 0.5-1h at 40-75 ℃ to obtain a mixture;
s3, adding styrene butadiene rubber, butadiene rubber and a plasticizer into an open mill, and mixing for 8-20min at 50-80 ℃;
and S4, adding the anti-aging agent, the vulcanizing agent, the accelerator and the mixture obtained in the step S2 into an open mill, mixing with the product obtained in the step 2), and mixing for 15-60min at 75-95 ℃ to obtain the ultra-hard wear-resistant rubber compound.
Preferably, the plasticizer is silicone oil, the anti-aging agent is a mixture of one or more of anti-aging agents MB, RD and 4010NA, the vulcanizing agent is sulfur, and the accelerator is a mixture of one or more of accelerators TT, NS and TMTD.
The invention has the beneficial effects that:
according to the invention, the composite modified reinforcing agent is formed by the carbon fiber, the nano zirconia, the rare earth element and the organic matter, and is used as a reinforcing filler to be added into a rubber compound matrix, so that the hardness and the wear resistance of the rubber compound can be greatly improved;
in the invention, the ZrO is formed by constructing carbon fiber loaded nano zirconia, modifying by rare earth elements and further grafting organic matters 2 The @ CNF-RE-organic matter system obtains a composite modified reinforcing agent capable of simultaneously solving the application problem of carbon fiber and nano zirconia in an organic matrix, and obviously improves the performances of hardness, wear resistance and the like of rubber compound through the synergistic enhancement in multiple aspects.
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 conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides an ultra-hard wear-resistant rubber compound which is prepared from the following raw materials in parts by weight:
60-92 parts of styrene butadiene rubber;
43-75 parts of butadiene rubber;
8-24 parts of polyether-ether-ketone;
22-46 parts of composite modified reinforcing agent;
1.5-4 parts of stearic acid;
2-8.5 parts of zinc oxide;
3-6 parts of a plasticizer;
1.2-3 parts of anti-aging agent;
1.6-5 parts by weight of a vulcanizing agent;
0.5 to 3 weight portions of accelerant.
In a preferred embodiment, the plasticizer is silicone oil, the anti-aging agent is a mixture of one or more of anti-aging agents MB, RD and 4010NA, the vulcanizing agent is sulfur, and the accelerator is a mixture of one or more of accelerators TT, NS and TMTD.
In a preferred embodiment, the ultra-hard and wear-resistant rubber compound is prepared by the following method:
s1, weighing raw materials according to the weight part ratio;
s2, adding polyether-ether-ketone, a composite modified reinforcing agent, stearic acid and zinc oxide into a mixer, and stirring for 0.5-1h at 40-75 ℃ to obtain a mixture;
s3, adding styrene butadiene rubber, butadiene rubber and a plasticizer into an open mill, and mixing for 8-20min at 50-80 ℃;
and S4, adding the anti-aging agent, the vulcanizing agent, the accelerator and the mixture obtained in the step S2 into an open mill, mixing with the product obtained in the step 2), and mixing for 15-60min at 75-95 ℃ to obtain the ultra-hard wear-resistant rubber compound.
In a preferred embodiment, the composite modified reinforcing agent is prepared by the following method:
1) Preparing acidified carbon fiber CNF:
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 neutrality, and vacuum drying for 8-20h to obtain the acidified carbon fiber CNF.
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) Preparation of rare earth-modified carbon fiber-zirconia composite ZrO 2 @CNF-RE：
2-1) adding a rare earth compound into ethanol to prepare a rare earth additive solution with the mass concentration of 0.05-1.2%;
the rare earth compound is a mixture of lanthanum chloride and yttrium chloride, and the mass ratio of lanthanum chloride to yttrium chloride is 2;
2-2) adding 0.5-4g of acidified carbon fibers, the rare earth additive solution and the organic zirconium salt 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;
wherein, the mass of the rare earth is 0.5-4.5% of that of the acidified carbon fiber;
wherein the mass ratio of the added zirconium ions to the acidified carbon fibers is 5-2;
wherein the organic zirconium salt is selected from one of zirconium acetate, zirconium n-propoxide, zirconium n-butoxide and zirconium citrate;
2-3) stirring the product obtained in the step 2) for 5-30min, heating to 65-85 ℃, dropwise adding a 65-85 ℃ sodium hydroxide solution into the product under continuous stirring until the precipitate in a reaction system is not increased any more, stopping dropwise adding, filtering, washing a solid product to be neutral, sintering for 2-6h at 450-750 ℃ under the protection of argon, cooling, and grinding to obtain the carbon fiber-zirconium oxide compound ZrO 2 2 @CNF-RE。
3) Using ZrO 2 Mixing @ CNF-RE with ammonium chloride and 1, 3-bis (hydroxymethyl) imidazolidine-2-thione to prepare a composite modified reinforcing agent:
3-1) reacting ZrO 2 Adding @ CNF-RE into ethanol, and performing ultrasonic treatment for 20-60min to obtain solution A;
3-2) adding ammonium chloride and 1, 3-bis (hydroxymethyl) imidazolidine-2-thione into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 0.5-2h at 40-60 ℃, standing for 2-6h, centrifuging, washing a solid product, and vacuum drying at 45-65 ℃ to obtain a composite modified reinforcing agent;
wherein, the added mass of the 1, 3-bis (hydroxymethyl) imidazolidine-2-thioketone is ZrO 2 1-4 times of @ CNF-RE, and the addition amount of ammonium chloride is ZrO 2 @ CNF-RE 5-8% by mass.
The nano zirconia has high strength and high stability, and is usually used as a reinforcing phase to improve the wear resistance, hardness and the like of materials based on excellent mechanical properties. 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.
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. Similarly, the nano zirconia has similar problems when used in an organic matrix material, and has nano size, large specific surface area, poor compatibility with an organic system and easy agglomeration, so that the nano zirconia is difficult to be uniformly dispersed in the organic system to fully exert the reinforcing performance of the nano zirconia.
The invention constructs carbon fiber loaded nano zirconia, modifies the carbon fiber loaded nano zirconia by rare earth elements and further grafts organic matters to form ZrO 2 The @ CNF-RE-organic system obtains a composite modified reinforcing agent, can simultaneously solve the application problem of carbon fiber and nano zirconia in an organic matrix, can also obviously improve the performances such as hardness, wear resistance and the like of rubber compound through multi-aspect synergistic enhancement, and details are provided in the following for the mechanism of the composite modified reinforcing agent.
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 (lanthanum and yttrium) 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, zirconium ions in the system are combined with oxygen-containing active groups through electrostatic action, so that the zirconium ions are also combined 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 zirconium ions on the surface of the carbon fiber; then, calcining to enable rare earth lanthanum, yttrium and zirconium ions to form stable oxides and firmly connect the oxides on the surface of the carbon fiber; and finally, by means of the bridging effect of rare earth elements, grafting an organic matter 1, 3-bis (hydroxymethyl) imidazolidine-2-thioketone on the surface of the carbon fiber, further introducing an active group containing oxygen, nitrogen and sulfur into the surface of the carbon fiber, and finally obtaining the carbon fiber-nano zirconia compound with the surface chemical activity remarkably improved, so that the improvement effects of the carbon fiber and the nano zirconia on the strength, the wear resistance and the hardness of the rubber compound can be greatly improved.
According to the invention, a composite structure system of carbon fibers and nano-zirconia is constructed, and the carbon fibers can be mutually overlapped in a matrix to form a three-dimensional network structure, so that the strength and hardness of the matrix are enhanced; the nano zirconia grafted on the carbon fiber can become a connection point of a three-dimensional network structure, so that the strength of the network structure can be improved; in the friction process, the carbon fiber can be used as a main bearing phase, and the zirconia particles can become strengthening points, so that the failure of the carbon fiber can be inhibited, and the wear resistance can be effectively improved. On the other hand, the carbon fiber is used as a carrier, so that the nano zirconia is uniformly loaded on the surface of the carbon fiber, and the aggregation of nano zirconia particles can be reduced, so that the uniform dispersion of the nano zirconia particles can be realized.
In the invention, the rare earth lanthanum and yttrium are introduced into the carbon fiber-nano zirconia composite structure system to play at least the following roles:
(1) The rare earth lanthanum and yttrium can activate the surface of the carbon fiber, improve the number 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, and rare earth lanthanum and yttrium form rare earth coordination bonds with the oxygen-containing functional groups and the organic matrix system, and are used as bridges to connect the carbon fiber and the organic matrix, so that the interface connection strength can be greatly improved, and the mechanical property of the material is improved;
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 lanthanum and yttrium atoms have high proton number, so that the attraction to electrons is strong, and the content of active groups on the surface of the carbon fiber can be effectively improved;
(2) The compounding of lanthanum and yttrium can play a role in synergistic enhancement in the reinforcing effect, and the introduced yttrium oxide can also play a role in stabilizing the crystalline phase state of zirconium oxide, so that the reinforcing effect of zirconium oxide can be further improved;
(3) The rare earth lanthanum and yttrium have large and many coordination numbers, and after forming a complex with oxygen-containing functions on the surface of carbon fibers, organic 1, 3-bis (hydroxymethyl) imidazolidine-2-thioketone can be grafted to the surface of the carbon fibers (forming a mixed complex) through coordination, after being added into a rubber compound system, the complex formed by the 1, 3-bis (hydroxymethyl) imidazolidine-2-thioketone, lanthanum and yttrium can form mechanical anchors in an interface layer, and the anchors can play roles of enhancing mechanical properties and friction properties;
1, 3-bis (hydroxymethyl) imidazolidine-2-thiones, namely bis (hydroxymethyl) ethylenethiourea, having the following chemical formula (1):
formula (1)
The grafting of the 1, 3-bis (hydroxymethyl) imidazolidine-2-thione leads nitrogen and sulfur-containing groups and more oxygen-containing groups to be introduced into the surface of the carbon fiber, and the carbon fiber becomes groups with higher chemical activity under the action of rare earth lanthanum and yttrium, and the chemical activity groups can generate chemical bonds through interfacial chemical reaction with a rubber compound matrix, so that on one hand, the compatibility of the carbon fiber and the matrix is further improved, the carbon fiber and the matrix can be fully and uniformly dispersed in the matrix, and on the other hand, the bonding strength of the carbon fiber and the matrix interface can be improved (for example, sulfur can promote a high molecular compound with a net-shaped molecular structure to be formed in the matrix, so that the strength is improved), and thus the overall mechanical performance of the rubber compound is improved.
The polyether-ether-ketone has the characteristics of high mechanical strength, excellent impact resistance and wear resistance and the like, and by adding the polyether-ether-ketone and compounding with the composite modified reinforcing agent, the invention can achieve the effect of synergistically enhancing the mechanical strength and wear resistance of rubber compound.
According to the invention, in the step 2-2), the acidified carbon fibers, the rare earth additive solution and the zirconium acetate solution are subjected to ball milling, so that rare earth ions and zirconium ions can be promoted to be uniformly and greatly combined on the surfaces of the acidified carbon fibers.
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.
Example 1
An ultra-hard wear-resistant rubber compound is prepared from the following raw materials in parts by weight:
76 parts of styrene butadiene rubber;
45 parts of butadiene rubber;
13 parts of polyether-ether-ketone;
32 parts of composite modified reinforcing agent;
2.6 parts by weight of stearic acid;
5.8 parts by weight of zinc oxide;
4 parts of a plasticizer;
1.9 parts of anti-aging agent;
2.2 parts by weight of a vulcanizing agent;
1.3 parts of accelerator.
Wherein the plasticizer is silicone oil, the anti-aging agent is anti-aging agent MB, the vulcanizing agent is sulfur, the accelerator is a mixture of accelerator TT and TMTD, and the mass ratio is 1.
In the embodiment, the ultra-hard wear-resistant rubber compound is prepared by the following method:
s1, weighing raw materials according to the weight part ratio;
s2, adding polyether-ether-ketone, a composite modified reinforcing agent, stearic acid and zinc oxide into a mixer, and stirring for 1h at 65 ℃ to obtain a mixture;
s3, adding styrene butadiene rubber, butadiene rubber and a plasticizer into an open mill, and mixing for 12min at 70 ℃;
and S4, adding the anti-aging agent, the vulcanizing agent, the accelerator and the mixture obtained in the step S2 into an open mill, mixing with the product obtained in the step 2), and mixing at 85 ℃ for 35min to obtain the ultra-hard wear-resistant rubber compound.
In this embodiment, the composite modified reinforcing agent is prepared by the following method:
1) Preparing acidified carbon fiber CNF:
adding 1g of carbon fiber (45 μm, beijing Deke island gold science and technology Co., ltd., the same below) into the mixed acid, and performing ultrasonic treatment at 70 ℃ for 3h; filtering, washing the solid product with deionized water to be neutral, and performing vacuum drying for 10h to obtain acidified carbon fiber CNF;
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) Preparation of rare earth-modified carbon fiber-zirconia composite ZrO 2 @CNF-RE：
2-1) adding a rare earth compound into ethanol to prepare a rare earth additive solution with the mass concentration of 0.5%; the rare earth compound is a mixture of lanthanum chloride and yttrium chloride, and the mass ratio of lanthanum chloride to yttrium chloride is 2.
2-2) adding 1g of acidified carbon fibers, the rare earth additive solution and the zirconium acetate solution (the mass concentration is 10%) into 400mL of acetone, and performing ultrasonic treatment for 20min to obtain a mixture, and performing ball milling for 2h;
wherein, the mass of the rare earth is 2.5 percent of that of the acidified carbon fiber;
wherein the mass ratio of the added zirconium ions to the acidified carbon fibers is 3;
2-3) stirring the product obtained in the step 2) for 10min, heating to 80 ℃, dropwise adding a sodium hydroxide solution at 80 ℃ 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 at 650 ℃ for 4h under the protection of argon, cooling, and grinding to obtain the carbon fiber-zirconium oxide compound ZrO 2 @CNF-RE。
3) Using ZrO 2 Mixing @ CNF-RE with ammonium chloride and 1, 3-bis (hydroxymethyl) imidazolidine-2-thione to prepare a composite modified reinforcing agent:
3-1) adding 2g of ZrO 2 Adding @ CNF-RE into 100mL ethanol, and performing ultrasonic treatment for 40min to obtain solution A;
3-2) adding 0.12g of ammonium chloride and 5g of 1, 3-bis (hydroxymethyl) imidazolidine-2-thione (purchased from gipsho chemical engineering science and technology, shanghai, co., ltd.) into 200mL of ethanol, and stirring to obtain solution B;
3-3) adding the liquid B into the liquid A, stirring for 2h at 45 ℃, standing for 4h, centrifuging, washing a solid product, and drying in vacuum at 55 ℃ to obtain the composite modified reinforcing agent.
Example 2
An ultra-hard wear-resistant rubber compound is prepared from the following raw materials in parts by weight:
76 parts of styrene butadiene rubber;
45 parts of butadiene rubber;
13 parts of polyether-ether-ketone;
37 parts by weight of composite modified reinforcing agent;
2.6 parts by weight of stearic acid;
5.8 parts by weight of zinc oxide;
4 parts of a plasticizer;
1.9 parts of anti-aging agent;
2.2 parts by weight of a vulcanizing agent;
1.3 parts of accelerator.
Wherein the plasticizer is silicone oil, the anti-aging agent is anti-aging agent MB, the vulcanizing agent is sulfur, the accelerator is a mixture of accelerator TT and TMTD, and the mass ratio is 1.
In the embodiment, the ultra-hard wear-resistant rubber compound is prepared by the following method:
s1, weighing raw materials according to the weight part ratio;
s2, adding polyether-ether-ketone, a composite modified reinforcing agent, stearic acid and zinc oxide into a mixer, and stirring for 1h at 65 ℃ to obtain a mixture;
s3, adding styrene butadiene rubber, butadiene rubber and a plasticizer into an open mill, and mixing for 12min at 70 ℃;
and S4, adding the anti-aging agent, the vulcanizing agent, the accelerator and the mixture obtained in the step S2 into an open mill, mixing with the product obtained in the step 2), and mixing at 85 ℃ for 35min to obtain the ultra-hard wear-resistant rubber compound.
In this embodiment, the composite modified reinforcing agent is prepared by the following method:
1) Preparing acidified carbon fiber CNF:
adding 1g of carbon fiber (45 μm, beijing Deke island gold science and technology Co., ltd., the same below) into the mixed acid, and performing ultrasonic treatment at 70 ℃ for 3h; filtering, washing the solid product with deionized water to be neutral, and performing vacuum drying for 10 hours to obtain acidified carbon fiber CNF;
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) Preparation of rare earth-modified carbon fiber-zirconia composite ZrO 2 @CNF-RE：
2-1) adding a rare earth compound into ethanol to prepare a rare earth additive solution with the mass concentration of 0.5%; the rare earth compound is a mixture of lanthanum chloride and yttrium chloride, and the mass ratio of lanthanum chloride to yttrium chloride is 2.
2-2) adding 1g of acidified carbon fibers, the rare earth additive solution and the zirconium acetate solution (the mass concentration is 10%) into 400mL of acetone, and performing ultrasonic treatment for 20min to obtain a mixture, and performing ball milling for 2h;
wherein the mass of the rare earth is 2.5 percent of that of the acidified carbon fiber;
wherein the mass ratio of the added zirconium ions to the acidified carbon fibers is 3;
2-3) stirring the product obtained in the step 2) for 10min, heating to 80 ℃, dropwise adding a sodium hydroxide solution at 80 ℃ into the product under continuous stirring until the precipitate in a reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering at 650 ℃ for 4h under the protection of argon, cooling, and grinding to obtain the carbon fiber-zirconia compound ZrO 2 2 @CNF-RE。
3) Using ZrO 2 Mixing @ CNF-RE with ammonium chloride and 1, 3-bis (hydroxymethyl) imidazolidine-2-thione to prepare a composite modified reinforcing agent:
3-1) adding 2g of ZrO 2 Adding @ CNF-RE into 100mL ethanol, and performing ultrasonic treatment for 40min to obtain solution A;
3-2) adding 0.12g of ammonium chloride and 5g of 1, 3-bis (hydroxymethyl) imidazolidine-2-thione into 200mL of ethanol, and stirring to obtain a solution B;
3-3) adding the liquid B into the liquid A, stirring for 2h at 45 ℃, standing for 4h, centrifuging, washing a solid product, and drying in vacuum at 55 ℃ to obtain the composite modified reinforcing agent.
Example 3
An ultra-hard wear-resistant rubber compound is prepared from the following raw materials in parts by weight:
76 parts of styrene butadiene rubber;
45 parts of butadiene rubber;
13 parts of polyether-ether-ketone;
37 parts of composite modified reinforcing agent;
2.6 parts by weight of stearic acid;
5.8 parts by weight of zinc oxide;
4 parts of a plasticizer;
1.9 parts of anti-aging agent;
2.2 parts by weight of a vulcanizing agent;
1.3 parts of accelerator.
Wherein the plasticizer is silicone oil, the anti-aging agent is anti-aging agent MB, the vulcanizing agent is sulfur, the accelerator is a mixture of accelerator TT and TMTD, and the mass ratio is 1.
In the embodiment, the ultra-hard wear-resistant rubber compound is prepared by the following method:
s1, weighing raw materials according to the weight part ratio;
s2, adding polyether-ether-ketone, a composite modified reinforcing agent, stearic acid and zinc oxide into a mixer, and stirring for 1h at 65 ℃ to obtain a mixture;
s3, adding styrene butadiene rubber, butadiene rubber and a plasticizer into an open mill, and mixing for 12min at 70 ℃;
and S4, adding the anti-aging agent, the vulcanizing agent, the accelerator and the mixture obtained in the step S2 into an open mill, mixing with the product obtained in the step 2), and mixing at 85 ℃ for 35min to obtain the ultra-hard wear-resistant rubber compound.
In this embodiment, the composite modified reinforcing agent is prepared by the following method:
1) Preparing acidified carbon fiber CNF:
adding 1g of carbon fiber (45 μm, beijing Deke island gold science and technology Co., ltd., the same below) into the mixed acid, and performing ultrasonic treatment at 70 ℃ for 3h; filtering, washing the solid product with deionized water to be neutral, and performing vacuum drying for 10h to obtain acidified carbon fiber CNF;
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) Preparation of rare earth-modified carbon fiber-zirconia composite ZrO 2 @CNF-RE：
2-1) adding a rare earth compound into ethanol to prepare a rare earth additive solution with the mass concentration of 0.5%; the rare earth compound is a mixture of lanthanum chloride and yttrium chloride, and the mass ratio of lanthanum chloride to yttrium chloride is 2.
2-2) adding 1g of acidified carbon fibers, the rare earth additive solution and the zirconium acetate solution (the mass concentration is 10%) into 400mL of acetone, and performing ultrasonic treatment for 20min to obtain a mixture, and performing ball milling for 2h;
wherein, the mass of the rare earth is 2.5 percent of that of the acidified carbon fiber;
wherein the mass ratio of the added zirconium ions to the acidified carbon fibers is 5;
2-3) stirring the product obtained in the step 2) for 10min, heating to 80 ℃, dropwise adding a sodium hydroxide solution at 80 ℃ into the product under continuous stirring until the precipitate in a reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering at 650 ℃ for 4h under the protection of argon, cooling, and grinding to obtain the carbon fiber-zirconia compound ZrO 2 2 @CNF-RE。
3) Using ZrO 2 Mixing @ CNF-RE with ammonium chloride and 1, 3-bis (hydroxymethyl) imidazolidine-2-thione to prepare a composite modified reinforcing agent:
3-1) adding 2g of ZrO 2 Adding @ CNF-RE into 100mL of ethanol, and performing ultrasonic treatment for 40min to obtain solution A;
3-2) adding 0.12g of ammonium chloride and 5g of 1, 3-bis (hydroxymethyl) imidazolidine-2-thione into 200mL of ethanol, and stirring to obtain a solution B;
3-3) adding the solution B into the solution A, stirring for 2h at 45 ℃, standing for 4h, centrifuging, washing a solid product, and drying in vacuum at 55 ℃ to obtain the composite modified reinforcing agent.
Example 4
An ultra-hard wear-resistant rubber compound is prepared from the following raw materials in parts by weight:
76 parts of styrene butadiene rubber;
45 parts of butadiene rubber;
13 parts of polyether-ether-ketone;
37 parts of composite modified reinforcing agent;
2.6 parts by weight of stearic acid;
5.8 parts by weight of zinc oxide;
4 parts of a plasticizer;
1.9 parts of anti-aging agent;
2.2 parts by weight of a vulcanizing agent;
1.3 parts of accelerator.
Wherein the plasticizer is silicone oil, the anti-aging agent is anti-aging agent MB, the vulcanizing agent is sulfur, the accelerator is a mixture of accelerator TT and TMTD, and the mass ratio is 1.
In the embodiment, the ultra-hard wear-resistant rubber compound is prepared by the following method:
s1, weighing raw materials according to the weight part ratio;
s2, adding polyether-ether-ketone, a composite modified reinforcing agent, stearic acid and zinc oxide into a mixer, and stirring for 1h at 65 ℃ to obtain a mixture;
s3, adding styrene butadiene rubber, butadiene rubber and a plasticizer into an open mill, and mixing for 12min at 70 ℃;
and S4, adding the anti-aging agent, the vulcanizing agent, the accelerator and the mixture obtained in the step S2 into an open mill, mixing with the product obtained in the step 2), and mixing at 85 ℃ for 35min to obtain the ultra-hard wear-resistant rubber compound.
In this embodiment, the composite modified reinforcing agent is prepared by the following method:
1) Preparing acidified carbon fiber CNF:
adding 1g of carbon fiber (45 μm, beijing Deke island gold science and technology Co., ltd., the same shall apply hereinafter) into the mixed acid, and performing ultrasonic treatment at 70 ℃ for 3 hours; filtering, washing the solid product with deionized water to be neutral, and performing vacuum drying for 10 hours to obtain acidified carbon fiber CNF;
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) Preparation of rare earth-modified carbon fiber-zirconia composite ZrO 2 @CNF-RE：
2-1) adding a rare earth compound into ethanol to prepare a rare earth additive solution with the mass concentration of 0.5%; the rare earth compound is a mixture of lanthanum chloride and yttrium chloride, and the mass ratio of the lanthanum chloride to the yttrium chloride is 2.
2-2) adding 1g of acidified carbon fibers, a rare earth additive solution and a zirconium acetate solution (the mass concentration is 10%) into 400mL of acetone, and performing ultrasonic treatment for 20min to obtain a mixture, and performing ball milling for 2h;
wherein, the mass of the rare earth is 2.5 percent of that of the acidified carbon fiber;
wherein the mass ratio of the added zirconium ions to the acidified carbon fibers is 4;
2-3) stirring the product obtained in the step 2) for 10min, heating to 80 ℃, dropwise adding a sodium hydroxide solution at 80 ℃ into the product under continuous stirring until the precipitate in a reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering at 650 ℃ for 4h under the protection of argon, cooling, and grinding to obtain the carbon fiber-zirconia compound ZrO 2 2 @CNF-RE。
3) Using ZrO 2 Mixing @ CNF-RE with ammonium chloride and 1, 3-bis (hydroxymethyl) imidazolidine-2-thione to prepare a composite modified reinforcing agent:
3-1) adding 2g of ZrO 2 Adding @ CNF-RE into 100mL ethanol, and performing ultrasonic treatment for 40min to obtain solution A;
3-2) adding 0.12g of ammonium chloride and 5g of 1, 3-bis (hydroxymethyl) imidazolidine-2-thione into 200mL of ethanol, and stirring to obtain a solution B;
3-3) adding the liquid B into the liquid A, stirring for 2h at 45 ℃, standing for 4h, centrifuging, washing a solid product, and drying in vacuum at 55 ℃ to obtain the composite modified reinforcing agent.
Comparative example 1
This example is substantially the same as example 2, except that: the rubber compound in the embodiment is prepared from the following raw materials in parts by weight:
76 parts of styrene butadiene rubber;
45 parts of butadiene rubber;
13 parts of polyether-ether-ketone;
28 parts of nano zirconia;
9 parts of carbon fiber;
0.3 part by weight of a rare earth compound;
2.6 parts by weight of stearic acid;
5.8 parts by weight of zinc oxide;
4 parts of a plasticizer;
1.9 parts of anti-aging agent;
2.2 parts by weight of a vulcanizing agent;
1.3 parts of accelerator.
The rare earth compound is a mixture of lanthanum chloride and yttrium chloride, and the mass ratio of lanthanum chloride to yttrium chloride is 2.
Comparative example 2
This example is substantially the same as example 2, except that:
in this example, the composite modified reinforcing agent is prepared by the following method:
1) Preparing acidified carbon fiber CNF:
adding 1g of carbon fiber (45 μm, beijing Deke island gold science and technology Co., ltd., the same below) into the mixed acid, and performing ultrasonic treatment at 70 ℃ for 3h; filtering, washing the solid product with deionized water to be neutral, and performing vacuum drying for 10h to obtain acidified carbon fiber CNF;
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 rare earth modified carbon fiber CNF-RE:
2-1) adding a rare earth compound into ethanol to prepare a rare earth additive solution with the mass concentration of 0.5%; the rare earth compound is a mixture of lanthanum chloride and yttrium chloride, and the mass ratio of the lanthanum chloride to the yttrium chloride is 2.
2-2) adding 1g of acidified carbon fiber and rare earth additive solution into 400mL of acetone, performing ultrasonic treatment for 20min, and performing ball milling on the obtained mixture for 2h;
wherein, the mass of the rare earth is 2.5 percent of that of the acidified carbon fiber;
2-3) stirring the product obtained in the step 2) for 10min, heating to 80 ℃, dropwise adding a sodium hydroxide solution at 80 ℃ 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 at 650 ℃ for 4h under the protection of argon, cooling, and grinding to obtain the carbon fiber-zirconium oxide compound CNF-RE.
3) Preparing a composite modified reinforcing agent by mixing CNF-RE with ammonium chloride and 1, 3-bis (hydroxymethyl) imidazolidine-2-thione:
3-1) adding 2g of CNF-RE into 100mL of ethanol, and carrying out ultrasonic treatment for 40min to obtain solution A;
3-2) adding 0.12g of ammonium chloride and 5g of 1, 3-bis (hydroxymethyl) imidazolidine-2-thione into 200mL of ethanol, and stirring to obtain a solution B;
3-3) adding the liquid B into the liquid A, stirring for 2h at 45 ℃, standing for 4h, centrifuging, washing a solid product, and drying in vacuum at 55 ℃ to obtain the composite modified reinforcing agent.
Comparative example 3
This example is substantially the same as example 2, except that:
in this example, the composite modified reinforcing agent is prepared by the following method:
adding 1g of carbon fiber (45 μm, beijing Deke island gold science and technology Co., ltd., the same shall apply hereinafter) into the mixed acid, and performing ultrasonic treatment at 70 ℃ for 3 hours; filtering, washing the solid product with deionized water to be neutral, and performing vacuum drying for 10h to obtain acidified carbon fiber CNF;
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) Preparation of carbon fiber-zirconia composite ZrO 2 @CNF：
2-1) adding 1g of acidified carbon fibers and a zirconium acetate solution (with the mass concentration of 10%) into 400mL of acetone, and performing ultrasonic treatment for 20min to obtain a mixture, and performing ball milling for 2h;
wherein the mass ratio of the added zirconium ions to the acidified carbon fibers is 3;
2-3) stirring the product obtained in the step 2) for 10min, heating to 80 ℃, dropwise adding a sodium hydroxide solution at 80 ℃ 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 at 650 ℃ for 4h under the protection of argon, cooling, and grinding to obtain the carbon fiber-zirconium oxide compound ZrO 2 @CNF。
3) Using ZrO 2 Mixing @ CNF with ammonium chloride and 1, 3-bis (hydroxymethyl) imidazolidine-2-thione to prepare a composite modified reinforcing agent:
3-1) adding 2g of ZrO 2 @ CNF is added into 100mL ethanol, and ultrasonic treatment is carried out for 40min to obtain solution A;
3-2) adding 0.12g of ammonium chloride and 5g of 1, 3-bis (hydroxymethyl) imidazolidine-2-thione into 200mL of ethanol, and stirring to obtain a solution B;
3-3) adding the solution B into the solution A, stirring for 2h at 45 ℃, standing for 4h, centrifuging, washing a solid product, and drying in vacuum at 55 ℃ to obtain the composite modified reinforcing agent.
Comparative example 4
This example is substantially the same as example 2, except that:
in this example, the composite modified reinforcing agent is prepared by the following method:
1) Preparing acidified carbon fiber CNF:
adding 1g of carbon fiber (45 μm, beijing Deke island gold science and technology Co., ltd., the same below) into the mixed acid, and performing ultrasonic treatment at 70 ℃ for 3h; filtering, washing the solid product with deionized water to be neutral, and performing vacuum drying for 10 hours to obtain acidified carbon fiber CNF;
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) Preparation of rare earth-modified carbon fiber-zirconia composite ZrO 2 @CNF-RE：
2-1) adding a rare earth compound into ethanol to prepare a rare earth additive solution with the mass concentration of 0.5%; the rare earth compound is a mixture of lanthanum chloride and yttrium chloride, and the mass ratio of lanthanum chloride to yttrium chloride is 2.
2-2) adding 1g of acidified carbon fibers, a rare earth additive solution and a zirconium acetate solution (the mass concentration is 10%) into 400mL of acetone, and performing ultrasonic treatment for 20min to obtain a mixture, and performing ball milling for 2h;
wherein the mass of the rare earth is 2.5 percent of that of the acidified carbon fiber;
wherein the mass ratio of the added zirconium ions to the acidified carbon fibers is 3;
2-3) stirring the product obtained in the step 2) for 10min, heating to 80 ℃, dropwise adding a sodium hydroxide solution at 80 ℃ into the product under continuous stirring until the precipitate in a reaction system is not increased any more, stopping dropwise adding, filtering, washing the solid product to be neutral, sintering at 650 ℃ for 4h under the protection of argon, cooling, and grinding to obtain the carbon fiber-zirconia compound ZrO 2 2 @ CNF-RE, which is used as a composite modifier reinforcement.
The mixes obtained in examples 1 to 4 and comparative examples 1 to 4 were vulcanized: performing primary vulcanization at 160 ℃ for 10min, and secondary vulcanization at 225 ℃ for 6h to obtain vulcanized rubber, and performing performance detection on the vulcanized rubber, wherein the detection items comprise:
shore A hardness: the detection standard GB-T531.1-2008;
tensile strength, elongation at break: the detection standard GB-T528-2009;
attorney abrasion: the detection standard GB-T1689-2014;
the results are shown in Table 1 below
TABLE 1
From the results of examples 1 to 4, it can be seen that the rubber compound prepared according to the present invention has ultra-high hardness and excellent abrasion resistance; in the comparative example 1, the nano zirconia, the carbon fiber and the rare earth compound are respectively added in the form of monomers, and the reinforcing effect of each monomer is difficult to fully exert due to the difficulty in fully dispersing in an organic system of rubber compound; in comparative example 2, no nano zirconia was introduced, and the hardness and wear resistance were reduced; in the comparative example 3, no rare earth element is introduced, so that the compatibility of the nano zirconia-carbon fiber system and a rubber compound organic system and the interface bonding strength are reduced, and the mechanical property is obviously reduced; comparative example 4 does not introduce 1, 3-bis (hydroxymethyl) imidazolidine-2-thione, so that the compatibility of the nano zirconia-carbon fiber structure with an organic system is reduced, and the mechanical properties of the rubber compound are reduced.
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 ultra-hard wear-resistant rubber compound is characterized by being prepared from the following raw materials in parts by weight:
60-92 parts of styrene butadiene rubber;
43-75 parts of butadiene rubber;
8-24 parts of polyether-ether-ketone;
22-46 parts of composite modified reinforcing agent;
1.5-4 parts of stearic acid;
2-8.5 parts of zinc oxide;
3-6 parts of a plasticizer;
1.2-3 parts of anti-aging agent;
1.6-5 parts by weight of a vulcanizing agent;
0.5 to 3 weight portions of accelerant.
2. The ultra-hard and wear-resistant rubber compound as claimed in claim 1, wherein said composite modified reinforcing agent is prepared by the following method:
1) Preparing acidified carbon fiber CNF;
2) Preparation of rare earth modified carbon fiber-zirconia composite ZrO 2 @CNF-RE；
3) Using ZrO 2 Mixing @ CNF-RE with ammonium chloride and 1, 3-bis (hydroxymethyl) imidazolidine-2-thionePreparing a composite modified reinforcing agent.
3. An ultra-hard and wear-resistant mix as claimed in claim 2, wherein said step 1) is in particular: 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 the acidified carbon fiber CNF.
4. An ultra-hard abrasion-resistant mix as claimed in claim 3, wherein said mix acid is a mixture of 95% by mass of sulfuric acid and 65% by mass of nitric acid, and the volume ratio of sulfuric acid to nitric acid is 3:1.
5. ultra-hard, wear-resistant mix as claimed in claim 2, characterized in that said step 2) comprises in particular:
2-1) adding the rare earth compound into ethanol to prepare a rare earth additive solution with the mass concentration of 0.05-1.2%;
2-2) adding 0.5-4g of acidified carbon fibers, a rare earth additive solution and an organic zirconium salt 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;
wherein, the mass of the rare earth is 0.5-4.5% of that of the acidified carbon fiber;
2-3) stirring the product obtained in the step 2) for 5-30min, heating to 65-85 ℃, dropwise adding a 65-85 ℃ sodium hydroxide solution into the product under continuous stirring until the precipitate in the reaction system is not increased any more, stopping dropwise adding, filtering, washing a solid product to be neutral, sintering for 2-6h at 450-750 ℃ under the protection of argon, cooling, and grinding to obtain the carbon fiber-zirconium oxide compound ZrO 2 @CNF-RE。
6. The ultra-hard and abrasion-resistant rubber compound according to claim 5, wherein the mass ratio of the zirconium ions to the acidified carbon fibers added in step 2-2) is 5.
7. The ultra-hard abrasion-resistant rubber compound as claimed in claim 6, wherein the rare earth compound is a mixture of lanthanum chloride and yttrium chloride, and the mass ratio of lanthanum chloride to yttrium chloride is 2.
8. Ultra-high-hardness abrasion-resistant mix according to claim 7, characterized in that said step 3) comprises in particular:
3-1) ZrO treatment 2 Adding @ CNF-RE into ethanol, and performing ultrasonic treatment for 20-60min to obtain solution A;
3-2) adding ammonium chloride and 1, 3-bis (hydroxymethyl) imidazolidine-2-thione into ethanol, and stirring to obtain solution B;
3-3) adding the solution B into the solution A, stirring for 0.5-2h at 40-60 ℃, standing for 2-6h, centrifuging, washing a solid product, and vacuum drying at 45-65 ℃ to obtain a composite modified reinforcing agent;
wherein, the added mass of the 1, 3-bis (hydroxymethyl) imidazolidine-2-thione is ZrO 2 1-4 times of @ CNF-RE, and the addition amount of ammonium chloride is ZrO 2 @ CNF-RE 5-8% by mass.
9. Ultra-hard, wear-resistant mix according to any of claims 1 to 8, characterized in that it is prepared by the following method:
s1, weighing raw materials according to the weight part ratio;
s2, adding polyether-ether-ketone, a composite modified reinforcing agent, stearic acid and zinc oxide into a mixer, and stirring for 0.5-1h at 40-75 ℃ to obtain a mixture;
s3, adding styrene butadiene rubber, butadiene rubber and a plasticizer into an open mill, and mixing for 8-20min at 50-80 ℃;
and S4, adding the anti-aging agent, the vulcanizing agent, the accelerator and the mixture obtained in the step S2 into an open mill, mixing with the product obtained in the step 2), and mixing for 15-60min at 75-95 ℃ to obtain the ultra-hard wear-resistant rubber compound.
10. An ultra-hard, abrasion-resistant rubber compound as claimed in claim 9, wherein said plasticizer is silicone oil, said anti-aging agent is a mixture of one or more of anti-aging agents MB, RD, 4010NA, said vulcanizing agent is sulfur, and said accelerator is a mixture of one or more of accelerators TT, NS, TMTD.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211317052.2A CN115627017A (en) | 2022-10-26 | 2022-10-26 | Ultra-high-hardness wear-resistant rubber compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211317052.2A CN115627017A (en) | 2022-10-26 | 2022-10-26 | Ultra-high-hardness wear-resistant rubber compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115627017A true CN115627017A (en) | 2023-01-20 |
Family
ID=84906864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211317052.2A Pending CN115627017A (en) | 2022-10-26 | 2022-10-26 | Ultra-high-hardness wear-resistant rubber compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115627017A (en) |
-
2022
- 2022-10-26 CN CN202211317052.2A patent/CN115627017A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 橡胶工业原材料与装备简明手册编审委员会: "《橡胶工业原材料与装备简明手册•原材料与工艺耗材手册》", vol. 1, 中国建材工业出版社, pages: 1125 - 1129 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111533923B (en) | Graphene-hard material base composite latex with high wear resistance and high cutting resistance and application thereof | |
| CN108035143B (en) | Method for simultaneously improving interface strength and toughness of carbon fiber epoxy composite material | |
| CN113652010B (en) | Rubber composite material filled with end group functionalized liquid rubber and mercapto silane coupling agent synergistically modified white carbon black and preparation method thereof | |
| CN105968588A (en) | Special conveyer belt for chemical fertilizer granulation tank | |
| CN115558179A (en) | High-strength flame-retardant modified composite rubber | |
| CN113980359B (en) | Modified MXene-loaded metal oxide composite and preparation method and application thereof | |
| JP3362894B2 (en) | Chitosan reinforced tire and method of mixing chitosan with elastomer | |
| CN109627502B (en) | Composite material of natural rubber and preparation method thereof | |
| CN115627017A (en) | Ultra-high-hardness wear-resistant rubber compound | |
| CN104231368A (en) | Molybdenum disulfide/ butadiene styrene rubber/ butadiene-vinylpyridine rubber nanocomposite material with high wear resistance | |
| CN106543510B (en) | A kind of high-damping rubber material and preparation method thereof | |
| CN112500619A (en) | Aramid fiber reinforced nitrile rubber composite material and preparation method thereof | |
| CN115073826B (en) | High-wear-resistance graphene modified natural rubber and preparation method thereof | |
| CN107936273A (en) | A kind of high-performance light composite material of carbon fiber enhancement resin base and preparation method thereof | |
| CN111471244A (en) | High-strength high-viscosity low-temperature-resistant chlorinated polyethylene rubber-based cable sheath material and preparation method thereof | |
| CN110092961B (en) | High-performance nonpolar rubber material and preparation method thereof | |
| CN111269470B (en) | Organic silicon emulsion modified wet-process wear-resistant rubber and preparation method thereof | |
| CN109306094B (en) | Preparation method of graphene rubber master batch | |
| CN115627018A (en) | Preparation method of ageing-resistant high-elasticity rubber compound | |
| CN114426707B (en) | High-performance rubber/graphene oxide composite material and preparation method thereof | |
| WO2020237354A1 (en) | Method for improving dispersion of metal oxide in rubber by the use of cellulose nanocrystals (cncs); and rubber composites comprising cncs | |
| CN115386149B (en) | Preparation process of high-wear-resistance rubber material | |
| CN115044098B (en) | Special composite auxiliary agent for toughening and reinforcing polypropylene | |
| CN111253643A (en) | Preparation method of graphene oxide reinforced styrene butadiene rubber material | |
| CN115612214B (en) | Low-Mooney high-hardness ethylene propylene diene monomer rubber composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |