CN119775787A - A recycled oil bio-based plastic mixed rubber sole material and preparation method thereof - Google Patents
A recycled oil bio-based plastic mixed rubber sole material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a regenerated oil bio-based plastic mixed rubber sole material which comprises, by mass, 40-60 parts of regenerated oil bio-based plastic, 20-30 parts of smoke rubber, 10-15 parts of modified mixed reinforced filler, 10-20 parts of calcium powder, 0.5-1.0 part of dicumyl oxide, 1.0-1.5 parts of zinc oxide, 0.5-0.8 part of stearic acid, 1.5-2.5 parts of octylated diphenylamine and 4-6 parts of antibacterial and mildew-proof filler, and relates to the technical field of rubber soles. According to the reclaimed oil bio-based plastic mixed rubber sole material and the preparation method thereof, the modified mixed reinforced filler and the modified antibacterial mildew-proof filler are added, so that the reclaimed oil bio-based plastic mixed rubber sole material can better adapt to the conditions of bending, deformation and the like of soles in the wearing process when being applied to the reclaimed oil bio-based plastic modified rubber sole material, and the wearing comfort and durability of the soles are improved. And the requirements of antibacterial effect are met, and the anti-cracking performance is also considered, so that the anti-cracking composite material can be better applied to the regenerated oil bio-based plastic mixed rubber sole material, and the comprehensive performance and the service life of the sole are improved.
Description
Technical Field
The invention relates to the technical field of rubber soles, in particular to a reclaimed oil bio-based plastic mixed rubber sole material and a preparation method thereof.
Background
The traditional sole material mainly comprises rubber, and the rubber has the advantages of good elasticity, wear resistance, skid resistance and the like, and can meet the basic requirements of soles in daily wear and various sports scenes. However, with increasing shortage of global resources and increasing awareness of environmental protection, conventional rubber sole materials face a number of challenges. In recent years, bio-based plastics have become increasingly popular as an emerging material. The bio-based plastic is derived from renewable biomass resources such as plant starch, cellulose and the like, and the production process of the bio-based plastic has lower carbon emission advantage than petroleum-based plastic, is beneficial to reducing dependence on petroleum resources, and accords with the ideas of green environmental protection and sustainable development. However, when bio-based plastics are used alone as sole materials, the mechanical properties thereof are insufficient in some aspects, such as strength, toughness and elastic recovery ability, which may be inferior to those of conventional rubbers, and it is difficult to completely satisfy the performance requirements of soles under complex stress conditions.
The reclaimed oil is used as a product of resource recycling, and has certain economic value and reusability. The method can be derived from various channels such as waste lubricating oil, animal and vegetable grease and the like, and the reclaimed oil is introduced into a sole material system, so that the recycling of wastes can be realized, and the processability and certain physical properties of the material can be improved.
The conventional rubber sole material has no antibacterial capability and low service life, and can not well adapt to bending and deformation in the wearing process, and has low wearing comfort and poor durability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a reclaimed oil bio-based plastic mixed rubber sole material and a preparation method thereof, and solves the problems.
The technical scheme is that the regenerated oil bio-based plastic mixed rubber sole material comprises, by mass, 40-60 parts of regenerated oil bio-based plastic, 20-30 parts of smoke gum, 10-15 parts of modified mixed reinforcing filler, 10-20 parts of calcium powder, 0.5-1.0 part of dicumyl oxide, 1.0-1.5 parts of zinc oxide, 0.5-0.8 part of stearic acid, 1.5-2.5 parts of octylated diphenylamine and 4-6 parts of antibacterial and mildew-proof filler;
the modified mixed reinforcing filler is prepared by the following steps:
A1, alkali washing and activating the fibers, and respectively soaking the bamboo fibers and the carbon fibers in potassium hydroxide solution for 1-1.5 hours at the soaking temperature of 40-45 ℃ to remove impurities on the surfaces of the fibers and generate active sites. Washing with a large amount of clear water to neutrality after soaking, and drying at 80-85deg.C for 2-2.5 hr;
A2, grafting a silane coupling agent, namely respectively adding the dried bamboo fiber and the dried carbon fiber into a silane coupling agent solution, wherein the mass ratio of the bamboo fiber to the silane coupling agent is 12:1-10:1, the mass ratio of the carbon fiber to the silane coupling agent is 15:1-13:1, stirring and reacting for 2-2.5 hours at 50-55 ℃, grafting the silane coupling agent on the surface of the fiber, enhancing the reactivity and compatibility of the fiber and a subsequent monomer, respectively filtering and washing the fiber after the reaction, and drying for 1-1.5 hours at 70-75 ℃;
A3, copolymerization grafting and crosslinking reaction, namely mixing bamboo fibers grafted by a silane coupling agent with carbon fibers, adding the mixture into toluene solution containing butyl acrylate, glycidyl methacrylate mixed monomers, an initiator azodiisobutyronitrile and a crosslinking agent polyethylene glycol diacrylate, stirring and reacting for 3-3.5 hours at 75-80 ℃ under the protection of nitrogen, and carrying out polymerization reaction on the mixed monomers and grafting the mixed monomers onto the surfaces of the fibers under the action of the initiator in the reaction process, wherein the crosslinking agent enables the grafted polymer chains to form a crosslinked structure, so that the performances of strength, toughness, heat resistance and the like of the fibers are improved. The long-chain alkyl structure of butyl acrylate is beneficial to increasing flexibility, the initiator is decomposed to generate free radicals, then the monomer is initiated to polymerize, the polymer chain is continuously increased and grafted on the surface of the fiber, and meanwhile, polyethylene glycol diacrylate participates in the crosslinking reaction, after the reaction is finished, the fiber is filtered and washed, and is dried for 1 to 1.5 hours at the temperature of 60 to 65 ℃;
A4, surface modification and dispersion treatment, namely placing the mixed fiber after copolymerization grafting into ethanol solution containing glycerol stearate, and stirring and reacting for 1.5-2 hours at 40-45 ℃. The glyceryl stearate is physically adsorbed or chemically bonded with active groups on the surface of the fiber or the grafted polymer to play roles in lubricating and improving dispersibility, and the ester structure of the glyceryl stearate is also beneficial to certain flexibility improvement. After the reaction is finished, filtering and washing the fiber, and drying for 1 to 1.5 hours at 50 to 55 ℃ to obtain the modified mixed reinforcing filler.
Preferably, the concentration of the silane coupling agent solution in the A2 is 2-3%, wherein the solvent is ethanol.
Preferably, the amount of the glycidyl methacrylate mixed monomer in the A3 is 25-35% of the total mass of the fiber, the amount of the initiator azo-bis-isobutyronitrile is 0.8-1.2% of the mass of the mixed monomer, and the amount of the cross-linking agent polyethylene glycol diacrylate is 0.4-0.8% of the mass of the mixed monomer.
Preferably, the content of the glyceryl stearate in the A4 is 4-8% of the total mass of the fiber, and the concentration of the ethanol solution is 4-8%.
Preferably, the antibacterial and mildew-proof filler comprises the following raw materials, by weight, 2-3 parts of nano copper oxide, 2-3 parts of trimethyl octadecyl silane quaternary ammonium salt, 3-4 parts of sepiolite powder and 0.5-1 part of vinyl triethoxysilane.
The antibacterial mildew-proof filler is prepared by the following steps:
B1, nano copper oxide surface modification, dispersing nano copper oxide in ethanol solution, carrying out ultrasonic treatment for 40-60 minutes to enable the nano copper oxide to be uniformly dispersed, then slowly dripping vinyl triethoxysilane, stirring at 40-45 ℃ for 2-3 hours, after the reaction is finished, centrifugally separating, washing 3-5 times by ethanol, and drying at 60-70 ℃ for 2-3 hours;
B2, the antibacterial agent and sepiolite powder are compounded, the organosilicon quaternary ammonium salt antibacterial agent is dissolved in toluene solution and added into the sepiolite powder, the mixture is stirred and reacted for 3 to 4 hours at 50 to 55 ℃, and the use amount of the antibacterial agent is 50 to 60 percent of the mass of the sepiolite powder. After the reaction, vacuum drying is carried out for 4 to 5 hours at the temperature of 80 to 90 ℃ so that the antibacterial agent is fully loaded in the pore structure of the sepiolite powder to form a composite carrier with the antibacterial function;
And B3, compounding and secondarily modifying the nano copper oxide with a composite carrier, adding the nano copper oxide with the surface modified into the antibacterial agent and sepiolite powder compound, adding ethanol, uniformly stirring, then dropwise adding gamma-aminopropyl triethoxysilane, and stirring and reacting for 2.5-3.5 hours at 45-50 ℃. After the reaction is finished, filtering, washing with ethanol for 2-4 times, and drying at 70-80 ℃ for 3-4 hours. The step further enhances the binding force between the nano copper oxide and the composite carrier, and simultaneously the introduction of the vinyl triethoxysilane is beneficial to improving the dispersibility of the filler in the sole material and has a certain improvement effect on the cracking resistance of the material;
B4, crosslinking modification, namely mixing the product obtained in the third step with isocyanate crosslinking agent in toluene solution, and stirring and reacting for 1.5-2.5 hours at 60-70 ℃. In the reaction process, the cross-linking agent reacts with active groups on the surface of the filler to form a cross-linked network structure, so that the integrity and stability of the filler are obviously improved, the cracking phenomenon is effectively prevented, and meanwhile, the antibacterial performance of the filler is not influenced. After the reaction is finished, the final modified antibacterial mildew-proof filler is obtained through filtering, washing and drying treatment.
Preferably, the concentration of the ethanol solution in the B1 is 6-8%, and the mass ratio of the vinyl triethoxysilane to the nano copper oxide is 1:4-1:3.
Preferably, the concentration of the toluene solution in the B2 is 10-15%.
Preferably, the concentration of the ethanol solution in the B3 is 6-8%, and the dosage of the gamma-aminopropyl triethoxysilane is 0.3-0.5% of the total mass.
Preferably, the isocyanate crosslinking agent in the B4 is toluene diisocyanate, the dosage is 1-2% of the total mass, the drying temperature is 80-90 ℃, and the drying time is 3-5 hours.
The preparation method of the reclaimed oil bio-based plastic mixed rubber sole material comprises the following steps:
s1, drying the reclaimed oil bio-based plastic under the conditions of constant temperature and constant humidity to remove water contained in the reclaimed oil bio-based plastic;
s2, adding the dried reclaimed oil bio-based plastic and the smoke rubber into an internal mixer or an open mill, setting the rotation speed of the internal mixer to be 30-50 r/min, setting the rotation speed of a roller of the open mill to be 10-15 r/min, controlling the mixing temperature to be 80-100 ℃, and firstly carrying out preliminary mixing for 5-10 min to uniformly mix the reclaimed oil bio-based plastic and the smoke rubber to form a continuous matrix phase;
S3, adding 10-15 parts of modified mixed reinforcing filler and calcium powder into the matrix, and continuing mixing for 10-15 minutes, wherein in the mixing process, the state of the material is observed to ensure that the filler is uniformly dispersed in the matrix material. The rotation speed and the temperature of the mixer are properly regulated, the rotation speed of the internal mixer can be increased to 50-70 rpm, the temperature is controlled to be 100-120 ℃, and the rotation speed of the roller of the open mill can be increased to 15-20 rpm.
S4, sequentially adding dicumyl oxide, zinc oxide, stearic acid, octylated diphenylamine and antibacterial mildew-proof filler, and mixing for 10-15 minutes. The mixing process is to ensure that the auxiliary agent is fully dispersed to avoid agglomeration, the rotating speed of the internal mixer is maintained at 60-80 r/min and the temperature is 120-140 ℃, the rotating speed of the roller of the open mill is 20-25 r/min, and uniform rubber compound is obtained after the mixing is completed;
S5, preforming the mixed rubber material according to the shape and size requirements of the sole, putting the preformed sole into a vulcanizing machine, setting the vulcanizing temperature to be 150-180 ℃, setting the vulcanizing pressure to be 10-15MPa, and setting the vulcanizing time to be 10-30 minutes. In the vulcanization process, the dicumyl oxide initiates a crosslinking reaction between rubber molecular chains, a stable crosslinking network structure is formed under the activation of zinc oxide and stearic acid, and meanwhile, the octylated diphenylamine plays an anti-aging role, and the antibacterial and mildew-proof filler plays an antibacterial and mildew-proof function.
And S6, taking out the sole from the vulcanizing machine after vulcanization is completed, and performing demolding operation.
The invention provides a reclaimed oil bio-based plastic mixed rubber sole material and a preparation method thereof. The beneficial effects are as follows:
The flexibility and elasticity of the reclaimed oil bio-based plastic and the natural rubber elasticity of the smoke rubber are combined with rebound resilience, so that the sole has good bending performance, can adapt to various deformation actions of feet during walking and movement, provides comfortable wearing experience, is not easy to crack or break after repeated bending, and ensures the durability of the sole.
By adding the modified mixed reinforcing filler, butyl acrylate monomer containing long-chain alkyl is used for replacing part of the original rigid monomer, and glyceryl stearate is used for surface treatment, and the flexibility of the whole modified mixed reinforcing filler is expected to be increased through adjustment and replacement of the functional groups, so that the modified mixed reinforcing filler can better adapt to the conditions of bending, deformation and the like of soles in the wearing process when being applied to reclaimed oil bio-based plastic modified rubber sole materials, and the wearing comfort and durability of the soles are improved.
The modified antibacterial mildew-proof filler prepared by the modification reaction fully plays antibacterial advantages of the nano copper oxide and the organosilicon quaternary ammonium salt antibacterial agent, and simultaneously effectively improves dispersibility, binding force with the material and cracking resistance of the filler in the sole material by virtue of the characteristics of sepiolite powder and multiple modification treatments, preferentially meets the requirement of antibacterial effect, and gives consideration to the cracking resistance, so that the modified antibacterial mildew-proof filler can be better applied to the reclaimed oil bio-based plastic mixed rubber sole material, and improves the comprehensive performance and service life of soles.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1,
The invention provides a technical scheme that the modified mixed reinforcing filler is prepared by the following steps:
a1, alkali washing and activating the fibers, and respectively soaking the bamboo fibers and the carbon fibers in potassium hydroxide solution for 1 hour at a soaking temperature of 40 ℃ to remove impurities on the surfaces of the fibers and generate active sites. Washing the soaked materials with a large amount of clear water to be neutral, and drying the materials at 80 ℃ for 2 hours;
A2, grafting a silane coupling agent, namely respectively adding the dried bamboo fiber and the dried carbon fiber into a silane coupling agent solution, wherein the mass ratio of the bamboo fiber to the silane coupling agent is 12:1, the mass ratio of the carbon fiber to the silane coupling agent is 15:1, stirring and reacting for 2 hours at 50 ℃, grafting the silane coupling agent on the surface of the fiber, enhancing the reactivity and compatibility of the fiber and a subsequent monomer, respectively filtering and washing the fiber after the reaction, and drying for 1 hour at 70-75 ℃, wherein the concentration of the silane coupling agent solution is 2%, and the solvent is ethanol.
A3, copolymerization grafting and crosslinking reaction, namely mixing bamboo fibers grafted by a silane coupling agent with carbon fibers, adding the mixture into a toluene solution containing butyl acrylate, glycidyl methacrylate mixed monomers, an initiator azo-diisobutyronitrile and a crosslinking agent polyethylene glycol diacrylate, stirring and reacting for 3 hours at 75 ℃ under the protection of nitrogen, and carrying out polymerization reaction on the mixed monomers and grafting the mixed monomers onto the surfaces of the fibers under the action of the initiator in the reaction process, wherein the crosslinking agent enables the grafted polymer chains to form a crosslinked structure, so that the performances of strength, toughness, heat resistance and the like of the fibers are improved. The long-chain alkyl structure of butyl acrylate is beneficial to increasing flexibility, an initiator is decomposed to generate free radicals, then the monomer is initiated to polymerize, a polymer chain is continuously increased and grafted on the surface of the fiber, meanwhile, polyethylene glycol diacrylate participates in a crosslinking reaction, after the reaction is finished, the fiber is filtered and washed, the fiber is dried for 1 hour at 60 ℃, the amount of glycidyl methacrylate mixed monomer is 25% of the total mass of the fiber, the amount of initiator azo-diisobutyronitrile is 0.8% of the mass of the mixed monomer, and the amount of crosslinking agent polyethylene glycol diacrylate is 0.4% of the mass of the mixed monomer.
A4, surface modification and dispersion treatment, namely placing the mixed fiber after copolymerization grafting into an ethanol solution containing glycerol stearate, and stirring and reacting for 1.5 hours at 40 ℃. The glyceryl stearate is physically adsorbed or chemically bonded with active groups on the surface of the fiber or the grafted polymer to play roles in lubricating and improving dispersibility, and the ester structure of the glyceryl stearate is also beneficial to certain flexibility improvement. After the reaction, the fiber was filtered and washed and dried at 50 ℃ for 1 hour to obtain a modified mixed reinforcing filler. The dosage of the glyceryl stearate is 4% of the total mass of the fiber, and the concentration of the ethanol solution is 4%.
EXAMPLE 2,
The invention provides a technical scheme that the modified mixed reinforcing filler is prepared by the following steps:
A1, alkali washing and activating the fibers, and respectively soaking the bamboo fibers and the carbon fibers in potassium hydroxide solution for 1.5 hours at the soaking temperature of 45 ℃ to remove impurities on the surfaces of the fibers and generate active sites. Washing the soaked materials with a large amount of clear water to be neutral, and drying the materials at 85 ℃ for 2.5 hours;
A2, grafting a silane coupling agent, namely respectively adding the dried bamboo fiber and the dried carbon fiber into a silane coupling agent solution, wherein the mass ratio of the bamboo fiber to the silane coupling agent is 10:1, the mass ratio of the carbon fiber to the silane coupling agent is 13:1, stirring and reacting for 2.5 hours at 55 ℃, grafting the silane coupling agent on the surface of the fiber, enhancing the reactivity and compatibility of the fiber and a subsequent monomer, respectively filtering and washing the fiber after the reaction, and drying for 1.5 hours at 75 ℃, wherein the concentration of the silane coupling agent solution is 3%, and the solvent is ethanol.
A3, copolymerization grafting and crosslinking reaction, namely mixing bamboo fibers grafted by a silane coupling agent with carbon fibers, adding the mixture into a toluene solution containing butyl acrylate, glycidyl methacrylate mixed monomers, an initiator azo-diisobutyronitrile and a crosslinking agent polyethylene glycol diacrylate, stirring and reacting for 3.5 hours at 80 ℃ under the protection of nitrogen, and carrying out polymerization reaction on the mixed monomers and grafting the mixed monomers onto the surfaces of the fibers under the action of the initiator in the reaction process, wherein the crosslinking agent enables the grafted polymer chains to form a crosslinked structure, so that the performances of strength, toughness, heat resistance and the like of the fibers are improved. The long-chain alkyl structure of butyl acrylate is beneficial to increasing flexibility, an initiator is decomposed to generate free radicals, then the monomer is initiated to polymerize, a polymer chain is continuously increased and grafted on the surface of the fiber, meanwhile, polyethylene glycol diacrylate participates in a crosslinking reaction, after the reaction is finished, the fiber is filtered and washed, the fiber is dried for 1.5 hours at 65 ℃, the amount of glycidyl methacrylate mixed monomer is 35% of the total mass of the fiber, the amount of initiator azodiisobutyronitrile is 1.2% of the mass of the mixed monomer, and the amount of crosslinking agent polyethylene glycol diacrylate is 0.8% of the mass of the mixed monomer.
A4, surface modification and dispersion treatment, namely placing the mixed fiber after copolymerization grafting into an ethanol solution containing glycerol stearate, and stirring and reacting for 2 hours at 45 ℃. The glyceryl stearate is physically adsorbed or chemically bonded with active groups on the surface of the fiber or the grafted polymer to play roles in lubricating and improving dispersibility, and the ester structure of the glyceryl stearate is also beneficial to certain flexibility improvement. After the reaction, the fiber was filtered and washed and dried at 55 ℃ for 1.5 hours to obtain a modified mixed reinforcing filler. The dosage of the glyceryl stearate is 8% of the total mass of the fiber, and the concentration of the ethanol solution is 8%.
EXAMPLE 3,
The invention provides a technical scheme that the antibacterial and mildew-proof filler comprises the following raw materials, by weight, 2 parts of nano copper oxide, 2 parts of trimethyl octadecyl silane quaternary ammonium salt, 3 parts of sepiolite powder and 0.5 part of vinyl triethoxysilane.
The antibacterial mildew-proof filler is prepared by the following steps:
B1, nano copper oxide surface modification, dispersing nano copper oxide in ethanol solution, carrying out ultrasonic treatment for 40 minutes to enable the nano copper oxide to be uniformly dispersed, then slowly dropwise adding vinyl triethoxysilane, stirring and reacting for 2 hours at 40 ℃, after the reaction is finished, centrifugally separating, washing with ethanol for 3 times, and drying for 2 hours at 60 ℃, wherein the concentration of the ethanol solution is 6%, the mass ratio of vinyl triethoxysilane to nano copper oxide is 1:4, grafting vinyl triethoxysilane on the surface of nano copper oxide, improving the compatibility and binding force of the nano copper oxide with organic antibacterial agents and sepiolite powder, and enhancing the stability of antibacterial fillers;
B2, compounding the antibacterial agent and sepiolite powder, dissolving the organosilicon quaternary ammonium salt antibacterial agent in toluene solution, wherein the concentration of the toluene solution is 10%, adding the toluene solution into the sepiolite powder, and stirring and reacting for 3 hours at 50 ℃, wherein the dosage of the antibacterial agent is 50% of the mass of the sepiolite powder. After the reaction, vacuum drying is carried out for 4 hours at 80 ℃ to enable the antibacterial agent to be fully loaded in the pore structure of the sepiolite powder, so as to form a composite carrier with antibacterial function;
And B3, compounding and secondarily modifying the nano copper oxide with a composite carrier, adding the nano copper oxide with the surface modified into the antibacterial agent and sepiolite powder compound, adding ethanol, uniformly stirring, then dropwise adding gamma-aminopropyl triethoxysilane, and stirring and reacting for 2.5 hours at 45 ℃. After the reaction was completed, filtration, washing with ethanol 2 times, and drying at 70 ℃ for 3 hours. The concentration of the ethanol solution is 6%, and the dosage of the gamma-aminopropyl triethoxysilane is 0.3% of the total mass. The step further enhances the binding force between the nano copper oxide and the composite carrier, and simultaneously the introduction of the vinyl triethoxysilane is beneficial to improving the dispersibility of the filler in the sole material and has a certain improvement effect on the cracking resistance of the material;
B4, crosslinking modification, namely mixing the product obtained in the third step with isocyanate crosslinking agent in toluene solution, and stirring and reacting for 1.5 hours at 60 ℃. The isocyanate crosslinking agent is toluene diisocyanate and is used in an amount of 1% by mass, the drying temperature is 80 ℃, and the drying time is 3 hours. In the reaction process, the cross-linking agent reacts with active groups on the surface of the filler to form a cross-linked network structure, so that the integrity and stability of the filler are obviously improved, the cracking phenomenon is effectively prevented, and meanwhile, the antibacterial performance of the filler is not influenced. After the reaction is finished, the final modified antibacterial mildew-proof filler is obtained through filtering, washing and drying treatment.
EXAMPLE 4,
The invention provides a technical scheme that the antibacterial mildew-proof filler comprises the following raw materials, by weight, 2.5 parts of nano copper oxide, 2.5 parts of trimethyl octadecyl silane quaternary ammonium salt, 3.5 parts of sepiolite powder and 0.8 part of vinyl triethoxysilane.
The antibacterial mildew-proof filler is prepared by the following steps:
B1, nano copper oxide surface modification, dispersing nano copper oxide in ethanol solution, carrying out ultrasonic treatment for 60 minutes to enable the nano copper oxide to be uniformly dispersed, then slowly dropwise adding vinyl triethoxysilane, stirring and reacting for 3 hours at 45 ℃, after the reaction is finished, centrifugally separating, washing with ethanol for 5 times, and drying for 3 hours at 70 ℃, wherein the concentration of the ethanol solution is 8%, the mass ratio of vinyl triethoxysilane to nano copper oxide is 1:3, grafting vinyl triethoxysilane on the surface of nano copper oxide, improving the compatibility and binding force of the nano copper oxide with organic antibacterial agents and sepiolite powder, and enhancing the stability of antibacterial fillers;
b2, compounding the antibacterial agent and sepiolite powder, dissolving the organosilicon quaternary ammonium salt antibacterial agent in toluene solution, wherein the concentration of the toluene solution is 15%, adding the toluene solution into the sepiolite powder, and stirring and reacting for 4 hours at 55 ℃, wherein the dosage of the antibacterial agent is 60% of the mass of the sepiolite powder. After the reaction, vacuum drying is carried out for 5 hours at 90 ℃ to enable the antibacterial agent to be fully loaded in the pore structure of the sepiolite powder, so as to form a composite carrier with antibacterial function;
And B3, compounding and secondarily modifying the nano copper oxide with a composite carrier, adding the nano copper oxide with the surface modified into the antibacterial agent and sepiolite powder compound, adding ethanol, uniformly stirring, then dropwise adding gamma-aminopropyl triethoxysilane, and stirring and reacting for 3.5 hours at 50 ℃. After the reaction was completed, filtration, washing with ethanol 4 times, and drying at 80 ℃ for 4 hours. The concentration of the ethanol solution is 8%, and the dosage of the gamma-aminopropyl triethoxysilane is 0.5% of the total mass. The step further enhances the binding force between the nano copper oxide and the composite carrier, and simultaneously the introduction of the vinyl triethoxysilane is beneficial to improving the dispersibility of the filler in the sole material and has a certain improvement effect on the cracking resistance of the material;
B4, crosslinking modification, namely mixing the product obtained in the third step with isocyanate crosslinking agent in toluene solution, and stirring and reacting for 2.5 hours at 70 ℃. The isocyanate crosslinking agent is toluene diisocyanate and is used in an amount of 2% of the total mass, the drying temperature is 90 ℃, and the drying time is 5 hours. In the reaction process, the cross-linking agent reacts with active groups on the surface of the filler to form a cross-linked network structure, so that the integrity and stability of the filler are obviously improved, the cracking phenomenon is effectively prevented, and meanwhile, the antibacterial performance of the filler is not influenced. After the reaction is finished, the final modified antibacterial mildew-proof filler is obtained through filtering, washing and drying treatment.
EXAMPLE 5,
The invention provides a technical scheme that the antibacterial and mildew-proof filler comprises the following raw materials, by weight, 3 parts of nano copper oxide, 3 parts of trimethyl octadecyl silane quaternary ammonium salt, 4 parts of sepiolite powder and 1 part of vinyl triethoxysilane.
The antibacterial mildew-proof filler is prepared by the following steps:
B1, nano copper oxide surface modification, dispersing nano copper oxide in ethanol solution, carrying out ultrasonic treatment for 60 minutes to enable the nano copper oxide to be uniformly dispersed, then slowly dropwise adding vinyl triethoxysilane, stirring and reacting for 3 hours at 45 ℃, after the reaction is finished, centrifugally separating, washing with ethanol for 5 times, and drying for 3 hours at 70 ℃, wherein the concentration of the ethanol solution is 8%, the mass ratio of vinyl triethoxysilane to nano copper oxide is 1:3, grafting vinyl triethoxysilane on the surface of nano copper oxide, improving the compatibility and binding force of the nano copper oxide with organic antibacterial agents and sepiolite powder, and enhancing the stability of antibacterial fillers;
b2, compounding the antibacterial agent and sepiolite powder, dissolving the organosilicon quaternary ammonium salt antibacterial agent in toluene solution, wherein the concentration of the toluene solution is 15%, adding the toluene solution into the sepiolite powder, and stirring and reacting for 4 hours at 55 ℃, wherein the dosage of the antibacterial agent is 60% of the mass of the sepiolite powder. After the reaction, vacuum drying is carried out for 5 hours at 90 ℃ to enable the antibacterial agent to be fully loaded in the pore structure of the sepiolite powder, so as to form a composite carrier with antibacterial function;
And B3, compounding and secondarily modifying the nano copper oxide with a composite carrier, adding the nano copper oxide with the surface modified into the antibacterial agent and sepiolite powder compound, adding ethanol, uniformly stirring, then dropwise adding gamma-aminopropyl triethoxysilane, and stirring and reacting for 3.5 hours at 50 ℃. After the reaction was completed, filtration, washing with ethanol 4 times, and drying at 80 ℃ for 4 hours. The concentration of the ethanol solution is 8%, and the dosage of the gamma-aminopropyl triethoxysilane is 0.5% of the total mass. The step further enhances the binding force between the nano copper oxide and the composite carrier, and simultaneously the introduction of the vinyl triethoxysilane is beneficial to improving the dispersibility of the filler in the sole material and has a certain improvement effect on the cracking resistance of the material;
B4, crosslinking modification, namely mixing the product obtained in the third step with isocyanate crosslinking agent in toluene solution, and stirring and reacting for 2.5 hours at 70 ℃. The isocyanate crosslinking agent is toluene diisocyanate and is used in an amount of 2% of the total mass, the drying temperature is 90 ℃, and the drying time is 5 hours. In the reaction process, the cross-linking agent reacts with active groups on the surface of the filler to form a cross-linked network structure, so that the integrity and stability of the filler are obviously improved, the cracking phenomenon is effectively prevented, and meanwhile, the antibacterial performance of the filler is not influenced. After the reaction is finished, the final modified antibacterial mildew-proof filler is obtained through filtering, washing and drying treatment.
EXAMPLE 6,
The invention provides a technical scheme that the regenerated oil bio-based plastic mixed rubber sole material comprises, by mass, 40 parts of regenerated oil bio-based plastic, 20 parts of smoke gum, 10 parts of modified mixed reinforced filler prepared in example 1, 10 parts of calcium powder, 0.5 part of dicumyl oxide, 1.0 part of zinc oxide, 0.5 part of stearic acid, 1.5 parts of octylated diphenylamine and 4 parts of antibacterial and mildew-proof filler prepared in example 3;
The preparation method of the reclaimed oil bio-based plastic mixed rubber sole material comprises the following steps:
s1, drying the reclaimed oil bio-based plastic under the conditions of constant temperature and constant humidity to remove water contained in the reclaimed oil bio-based plastic;
S2, adding the dried reclaimed oil bio-based plastic and the smoke rubber into an internal mixer or an open mill, setting the rotation speed of the internal mixer to be 30 revolutions per minute, setting the rotation speed of a roller of the open mill to be 10 revolutions per minute, and controlling the mixing temperature to be 80 ℃;
s3, adding 10 parts of modified mixed reinforcing filler and calcium powder into the matrix, and continuously mixing for 10 minutes, wherein in the mixing process, the state of the material is observed to ensure that the filler is uniformly dispersed in the matrix material. The rotation speed and the temperature of the mixer are properly regulated, the rotation speed of the internal mixer can be increased to 50 revolutions per minute, the temperature is controlled to be 100 ℃, and the rotation speed of the open mill roller can be increased to 15 revolutions per minute.
S4, sequentially adding dicumyl oxide, zinc oxide, stearic acid, octylated diphenylamine and an antibacterial mildew-proof filler, and mixing for 10 minutes. The mixing process is to ensure that the auxiliary agent is fully dispersed to avoid agglomeration, wherein the rotating speed of the internal mixer is maintained at 60 revolutions per minute and the temperature is 120 ℃, the rotating speed of the roller of the open mill is 20 revolutions per minute, and uniform rubber compound is obtained after the mixing is completed;
S5, preforming the mixed rubber material according to the shape and size requirements of the sole, putting the preformed sole into a vulcanizing machine, setting the vulcanizing temperature to be 150 ℃, setting the vulcanizing pressure to be 10MPa, and setting the vulcanizing time to be 10 minutes. In the vulcanization process, the dicumyl oxide initiates a crosslinking reaction between rubber molecular chains, a stable crosslinking network structure is formed under the activation of zinc oxide and stearic acid, and meanwhile, the octylated diphenylamine plays an anti-aging role, and the antibacterial and mildew-proof filler plays an antibacterial and mildew-proof function.
And S6, taking out the sole from the vulcanizing machine after vulcanization is completed, and performing demolding operation.
EXAMPLE 7,
The invention provides a technical scheme that the regenerated oil bio-based plastic mixed rubber sole material comprises, by mass, 50 parts of regenerated oil bio-based plastic, 25 parts of smoke rubber, 13 parts of modified mixed reinforced filler prepared in example 1, 15 parts of calcium powder, 0.8 part of dicumyl oxide, 1.3 parts of zinc oxide, 0.7 part of stearic acid, 2 parts of octylated diphenylamine and 5 parts of antibacterial and mildew-proof filler prepared in example 3;
The preparation method of the reclaimed oil bio-based plastic mixed rubber sole material comprises the following steps:
s1, drying the reclaimed oil bio-based plastic under the conditions of constant temperature and constant humidity to remove water contained in the reclaimed oil bio-based plastic;
S2, adding the dried reclaimed oil bio-based plastic and the smoke rubber into an internal mixer or an open mill, setting the rotating speed of the internal mixer to be 50 revolutions per minute, setting the rotating speed of a roller of the open mill to be 15 revolutions per minute, and controlling the mixing temperature to be 100 ℃;
s3, adding 15 parts of modified mixed reinforcing filler and calcium powder into the matrix, and continuously mixing for 15 minutes, wherein in the mixing process, the state of the material is observed to ensure that the filler is uniformly dispersed in the matrix material. The rotation speed and the temperature of the mixer are properly regulated, the rotation speed of the internal mixer can be increased to 70 revolutions per minute, the temperature is controlled to 120 ℃, and the rotation speed of the open mill roller can be increased to 20 revolutions per minute.
S4, sequentially adding dicumyl oxide, zinc oxide, stearic acid, octylated diphenylamine and an antibacterial mildew-proof filler, and mixing for 15 minutes. The mixing process is to ensure that the auxiliary agent is fully dispersed to avoid agglomeration, the rotating speed of the internal mixer is maintained at 80 rpm and the temperature is 140 ℃, the rotating speed of the roller of the open mill is 25 rpm, and uniform rubber compound is obtained after the mixing is completed;
S5, preforming the mixed rubber material according to the shape and size requirements of the sole, putting the preformed sole into a vulcanizing machine, setting the vulcanizing temperature to be 180 ℃, setting the vulcanizing pressure to be 15MPa, and setting the vulcanizing time to be 30 minutes. In the vulcanization process, the dicumyl oxide initiates a crosslinking reaction between rubber molecular chains, a stable crosslinking network structure is formed under the activation of zinc oxide and stearic acid, and meanwhile, the octylated diphenylamine plays an anti-aging role, and the antibacterial and mildew-proof filler plays an antibacterial and mildew-proof function.
And S6, taking out the sole from the vulcanizing machine after vulcanization is completed, and performing demolding operation.
EXAMPLE 8,
The invention provides a technical scheme that the regenerated oil bio-based plastic mixed rubber sole material comprises, by mass, 60 parts of regenerated oil bio-based plastic, 30 parts of smoke gum, 15 parts of modified mixed reinforcing filler prepared in example 1, 20 parts of calcium powder, 1.0 part of dicumyl oxide, 1.5 parts of zinc oxide, 0.8 part of stearic acid, 2.5 parts of octylated diphenylamine and 6 parts of antibacterial and mildew-proof filler prepared in example 3;
The preparation method of the reclaimed oil bio-based plastic mixed rubber sole material comprises the following steps:
s1, drying the reclaimed oil bio-based plastic under the conditions of constant temperature and constant humidity to remove water contained in the reclaimed oil bio-based plastic;
S2, adding the dried reclaimed oil bio-based plastic and the smoke rubber into an internal mixer or an open mill, setting the rotating speed of the internal mixer to be 50 revolutions per minute, setting the rotating speed of a roller of the open mill to be 15 revolutions per minute, and controlling the mixing temperature to be 100 ℃;
s3, adding 15 parts of modified mixed reinforcing filler and calcium powder into the matrix, and continuously mixing for 15 minutes, wherein in the mixing process, the state of the material is observed to ensure that the filler is uniformly dispersed in the matrix material. The rotation speed and the temperature of the mixer are properly regulated, the rotation speed of the internal mixer can be increased to 70 revolutions per minute, the temperature is controlled to 120 ℃, and the rotation speed of the open mill roller can be increased to 20 revolutions per minute.
S4, sequentially adding dicumyl oxide, zinc oxide, stearic acid, octylated diphenylamine and an antibacterial mildew-proof filler, and mixing for 15 minutes. The mixing process is to ensure that the auxiliary agent is fully dispersed to avoid agglomeration, the rotating speed of the internal mixer is maintained at 80 rpm and the temperature is 140 ℃, the rotating speed of the roller of the open mill is 25 rpm, and uniform rubber compound is obtained after the mixing is completed;
S5, preforming the mixed rubber material according to the shape and size requirements of the sole, putting the preformed sole into a vulcanizing machine, setting the vulcanizing temperature to be 180 ℃, setting the vulcanizing pressure to be 15MPa, and setting the vulcanizing time to be 30 minutes. In the vulcanization process, the dicumyl oxide initiates a crosslinking reaction between rubber molecular chains, a stable crosslinking network structure is formed under the activation of zinc oxide and stearic acid, and meanwhile, the octylated diphenylamine plays an anti-aging role, and the antibacterial and mildew-proof filler plays an antibacterial and mildew-proof function.
And S6, taking out the sole from the vulcanizing machine after vulcanization is completed, and performing demolding operation.
EXAMPLE 9,
The invention provides a technical scheme that the regenerated oil bio-based plastic mixed rubber sole material comprises, by mass, 40 parts of regenerated oil bio-based plastic, 20 parts of smoke gum, 10 parts of modified mixed reinforced filler prepared in example 2, 10 parts of calcium powder, 0.5 part of dicumyl oxide, 1.0 part of zinc oxide, 0.5 part of stearic acid, 1.5 parts of octylated diphenylamine and 4 parts of antibacterial and mildew-proof filler prepared in example 4;
The preparation method of the reclaimed oil bio-based plastic mixed rubber sole material comprises the following steps:
s1, drying the reclaimed oil bio-based plastic under the conditions of constant temperature and constant humidity to remove water contained in the reclaimed oil bio-based plastic;
S2, adding the dried reclaimed oil bio-based plastic and the smoke rubber into an internal mixer or an open mill, setting the rotation speed of the internal mixer to be 30 revolutions per minute, setting the rotation speed of a roller of the open mill to be 10 revolutions per minute, and controlling the mixing temperature to be 80 ℃;
s3, adding 10 parts of modified mixed reinforcing filler and calcium powder into the matrix, and continuously mixing for 10 minutes, wherein in the mixing process, the state of the material is observed to ensure that the filler is uniformly dispersed in the matrix material. The rotation speed and the temperature of the mixer are properly regulated, the rotation speed of the internal mixer can be increased to 50 revolutions per minute, the temperature is controlled to be 100 ℃, and the rotation speed of the open mill roller can be increased to 15 revolutions per minute.
S4, sequentially adding dicumyl oxide, zinc oxide, stearic acid, octylated diphenylamine and an antibacterial mildew-proof filler, and mixing for 10 minutes. The mixing process is to ensure that the auxiliary agent is fully dispersed to avoid agglomeration, wherein the rotating speed of the internal mixer is maintained at 60 revolutions per minute and the temperature is 120 ℃, the rotating speed of the roller of the open mill is 20 revolutions per minute, and uniform rubber compound is obtained after the mixing is completed;
S5, preforming the mixed rubber material according to the shape and size requirements of the sole, putting the preformed sole into a vulcanizing machine, setting the vulcanizing temperature to be 150 ℃, setting the vulcanizing pressure to be 10MPa, and setting the vulcanizing time to be 10 minutes. In the vulcanization process, the dicumyl oxide initiates a crosslinking reaction between rubber molecular chains, a stable crosslinking network structure is formed under the activation of zinc oxide and stearic acid, and meanwhile, the octylated diphenylamine plays an anti-aging role, and the antibacterial and mildew-proof filler plays an antibacterial and mildew-proof function.
And S6, taking out the sole from the vulcanizing machine after vulcanization is completed, and performing demolding operation.
EXAMPLE 10,
The invention provides a technical scheme that the regenerated oil bio-based plastic mixed rubber sole material comprises, by mass, 50 parts of regenerated oil bio-based plastic, 25 parts of smoke rubber, 13 parts of modified mixed reinforced filler prepared in example 2, 15 parts of calcium powder, 0.8 part of dicumyl oxide, 1.3 parts of zinc oxide, 0.7 part of stearic acid, 2 parts of octylated diphenylamine and 5 parts of antibacterial and mildew-proof filler prepared in example 4;
The preparation method of the reclaimed oil bio-based plastic mixed rubber sole material comprises the following steps:
s1, drying the reclaimed oil bio-based plastic under the conditions of constant temperature and constant humidity to remove water contained in the reclaimed oil bio-based plastic;
S2, adding the dried reclaimed oil bio-based plastic and the smoke rubber into an internal mixer or an open mill, setting the rotating speed of the internal mixer to be 50 revolutions per minute, setting the rotating speed of a roller of the open mill to be 15 revolutions per minute, and controlling the mixing temperature to be 100 ℃;
s3, adding 15 parts of modified mixed reinforcing filler and calcium powder into the matrix, and continuously mixing for 15 minutes, wherein in the mixing process, the state of the material is observed to ensure that the filler is uniformly dispersed in the matrix material. The rotation speed and the temperature of the mixer are properly regulated, the rotation speed of the internal mixer can be increased to 70 revolutions per minute, the temperature is controlled to 120 ℃, and the rotation speed of the open mill roller can be increased to 20 revolutions per minute.
S4, sequentially adding dicumyl oxide, zinc oxide, stearic acid, octylated diphenylamine and an antibacterial mildew-proof filler, and mixing for 15 minutes. The mixing process is to ensure that the auxiliary agent is fully dispersed to avoid agglomeration, the rotating speed of the internal mixer is maintained at 80 rpm and the temperature is 140 ℃, the rotating speed of the roller of the open mill is 25 rpm, and uniform rubber compound is obtained after the mixing is completed;
S5, preforming the mixed rubber material according to the shape and size requirements of the sole, putting the preformed sole into a vulcanizing machine, setting the vulcanizing temperature to be 180 ℃, setting the vulcanizing pressure to be 15MPa, and setting the vulcanizing time to be 30 minutes. In the vulcanization process, the dicumyl oxide initiates a crosslinking reaction between rubber molecular chains, a stable crosslinking network structure is formed under the activation of zinc oxide and stearic acid, and meanwhile, the octylated diphenylamine plays an anti-aging role, and the antibacterial and mildew-proof filler plays an antibacterial and mildew-proof function.
And S6, taking out the sole from the vulcanizing machine after vulcanization is completed, and performing demolding operation.
EXAMPLE 11,
The invention provides a technical scheme that the regenerated oil bio-based plastic mixed rubber sole material comprises, by mass, 60 parts of regenerated oil bio-based plastic, 30 parts of smoke gum, 15 parts of modified mixed reinforcing filler prepared in example 1, 20 parts of calcium powder, 1.0 part of dicumyl oxide, 1.5 parts of zinc oxide, 0.8 part of stearic acid, 2.5 parts of octylated diphenylamine and 6 parts of antibacterial and mildew-proof filler prepared in example 4;
The preparation method of the reclaimed oil bio-based plastic mixed rubber sole material comprises the following steps:
s1, drying the reclaimed oil bio-based plastic under the conditions of constant temperature and constant humidity to remove water contained in the reclaimed oil bio-based plastic;
S2, adding the dried reclaimed oil bio-based plastic and the smoke rubber into an internal mixer or an open mill, setting the rotating speed of the internal mixer to be 50 revolutions per minute, setting the rotating speed of a roller of the open mill to be 15 revolutions per minute, and controlling the mixing temperature to be 100 ℃;
s3, adding 15 parts of modified mixed reinforcing filler and calcium powder into the matrix, and continuously mixing for 15 minutes, wherein in the mixing process, the state of the material is observed to ensure that the filler is uniformly dispersed in the matrix material. The rotation speed and the temperature of the mixer are properly regulated, the rotation speed of the internal mixer can be increased to 70 revolutions per minute, the temperature is controlled to 120 ℃, and the rotation speed of the open mill roller can be increased to 20 revolutions per minute.
S4, sequentially adding dicumyl oxide, zinc oxide, stearic acid, octylated diphenylamine and an antibacterial mildew-proof filler, and mixing for 15 minutes. The mixing process is to ensure that the auxiliary agent is fully dispersed to avoid agglomeration, the rotating speed of the internal mixer is maintained at 80 rpm and the temperature is 140 ℃, the rotating speed of the roller of the open mill is 25 rpm, and uniform rubber compound is obtained after the mixing is completed;
S5, preforming the mixed rubber material according to the shape and size requirements of the sole, putting the preformed sole into a vulcanizing machine, setting the vulcanizing temperature to be 180 ℃, setting the vulcanizing pressure to be 15MPa, and setting the vulcanizing time to be 30 minutes. In the vulcanization process, the dicumyl oxide initiates a crosslinking reaction between rubber molecular chains, a stable crosslinking network structure is formed under the activation of zinc oxide and stearic acid, and meanwhile, the octylated diphenylamine plays an anti-aging role, and the antibacterial and mildew-proof filler plays an antibacterial and mildew-proof function.
And S6, taking out the sole from the vulcanizing machine after vulcanization is completed, and performing demolding operation.
Comparative example 1, this comparative example, was a reclaimed oil bio-based plastic compounded rubber sole material, differing from example 7 in that no modified compounded reinforcing filler was added, and the remainder were the same.
Comparative example 2, this comparative example, was a reclaimed oil bio-based plastic mixed rubber sole material, differing from example 7 in that no antibacterial and mildew-proof filler was added, and the remainder were the same.
The performance of the reclaimed oil bio-based plastic mixed rubber sole materials prepared in examples 6 to 8 and comparative examples 1 to 2 was tested, and the test results are shown in table 1:
table 1:
As can be seen from Table 1, the regenerated oil bio-based plastic mixed rubber sole material of the invention is added with the antibacterial and mildew-proof filler, inhibits the growth and propagation of bacteria, endows the material with reliable antibacterial performance, improves antibacterial and bacteriostatic capabilities, enhances the comprehensive performance and service life of the sole, and can better adapt to the conditions of bending, deformation and the like of the sole in the wearing process and improve the wearing comfort and durability of the sole by adding the modified mixed reinforcing filler.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without more in the limited case. The term "comprising" an element defined by the term "comprising" does not exclude the presence of other identical elements in a process, method, article or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The regenerated oil bio-based plastic mixed rubber sole material is characterized by comprising, by mass, 40-60 parts of regenerated oil bio-based plastic, 20-30 parts of smoke rubber, 10-15 parts of modified mixed reinforced filler, 10-20 parts of calcium powder, 0.5-1.0 part of dicumyl oxide, 1.0-1.5 parts of zinc oxide, 0.5-0.8 part of stearic acid, 1.5-2.5 parts of octylated diphenylamine and 4-6 parts of antibacterial and mildew-proof filler;
the modified mixed reinforcing filler is prepared by the following steps:
A1, alkali washing and activating fibers, namely respectively soaking bamboo fibers and carbon fibers in potassium hydroxide solution for 1-1.5 hours at the soaking temperature of 40-45 ℃, respectively washing the soaked fibers with a large amount of clear water to be neutral, and then drying the soaked fibers and the carbon fibers at 80-85 ℃ for 2-2.5 hours;
A2, grafting a silane coupling agent, namely respectively adding the dried bamboo fiber and the dried carbon fiber into a silane coupling agent solution, wherein the mass ratio of the bamboo fiber to the silane coupling agent is 12:1-10:1, the mass ratio of the carbon fiber to the silane coupling agent is 15:1-13:1, stirring and reacting for 2-2.5 hours at 50-55 ℃, respectively filtering and washing the fiber after the reaction, and drying for 1-1.5 hours at 70-75 ℃;
A3, copolymerization grafting and crosslinking reaction, namely mixing bamboo fibers grafted by a silane coupling agent with carbon fibers, adding the mixture into toluene solution containing butyl acrylate, glycidyl methacrylate mixed monomers, an initiator azodiisobutyronitrile and a crosslinking agent polyethylene glycol diacrylate, stirring and reacting for 3-3.5 hours at 75-80 ℃ under the protection of nitrogen, decomposing the initiator to generate free radicals, then initiating monomer polymerization, continuously growing polymer chains and grafting the polymer chains onto the surfaces of the fibers, and simultaneously enabling polyethylene glycol diacrylate to participate in the crosslinking reaction;
A4, carrying out surface modification and dispersion treatment, putting the mixed fiber after copolymerization grafting into ethanol solution containing glycerol stearate, stirring and reacting for 1.5-2 hours at 40-45 ℃, filtering and washing the fiber after the reaction is finished, and drying for 1-1.5 hours at 50-55 ℃ to obtain the modified mixed reinforced filler.
2. The reclaimed oil bio-based plastic mixed rubber sole material according to claim 1, wherein the concentration of the silane coupling agent solution in the A2 is 2-3%, and the solvent is ethanol.
3. The reclaimed oil bio-based plastic mixed rubber sole material according to claim 1, wherein the amount of the glycidyl methacrylate mixed monomer in the A3 is 25-35% of the total mass of the fiber, the amount of the azo-bis-isobutyronitrile initiator is 0.8-1.2% of the mass of the mixed monomer, and the amount of the polyethylene glycol diacrylate cross-linking agent is 0.4-0.8% of the mass of the mixed monomer.
4. The reclaimed oil bio-based plastic mixed rubber sole material according to claim 1, wherein the amount of the glyceryl stearate in the A4 is 4-8% of the total mass of the fiber, and the concentration of the ethanol solution is 4-8%.
5. The reclaimed oil bio-based plastic mixed rubber sole material according to claim 1 is characterized in that the antibacterial and mildew-proof filler is composed of, by weight, 2-3 parts of nano copper oxide, 2-3 parts of trimethyl octadecyl silane quaternary ammonium salt, 3-4 parts of sepiolite powder and 0.5-1 part of vinyl triethoxysilane;
the antibacterial mildew-proof filler is prepared by the following steps:
B1, nano copper oxide surface modification, dispersing nano copper oxide in ethanol solution, carrying out ultrasonic treatment for 40-60 minutes to enable the nano copper oxide to be uniformly dispersed, then slowly dripping vinyltriethoxysilane, stirring at 40-45 ℃ for reaction for 2-3 hours, centrifuging after the reaction is finished, washing 3-5 times by ethanol, and drying at 60-70 ℃ for 2-3 hours;
b2, compounding an antibacterial agent and sepiolite powder, dissolving an organosilicon quaternary ammonium salt antibacterial agent in toluene solution, adding the solution into the sepiolite powder, stirring and reacting for 3-4 hours at 50-55 ℃, wherein the amount of the antibacterial agent is 50-60% of the mass of the sepiolite powder, and vacuum drying for 4-5 hours at 80-90 ℃ after the reaction;
B3, compounding and secondarily modifying the nano copper oxide with a composite carrier, adding the nano copper oxide with the surface modified into the antibacterial agent and sepiolite powder compound, adding ethanol, uniformly stirring, then dropwise adding gamma-aminopropyl triethoxysilane, stirring and reacting for 2.5-3.5 hours at 45-50 ℃, filtering after the reaction is finished, washing for 2-4 times with ethanol, and drying for 3-4 hours at 70-80 ℃;
And B4, crosslinking modification, namely mixing the product obtained in the third step with an isocyanate crosslinking agent in toluene solution, stirring and reacting for 1.5-2.5 hours at 60-70 ℃, and filtering, washing and drying after the reaction is finished to obtain the final modified antibacterial mildew-proof filler.
6. The reclaimed oil bio-based plastic mixed rubber sole material according to claim 5, wherein the concentration of the ethanol solution in the B1 is 6-8%, and the mass ratio of the vinyl triethoxysilane to the nano copper oxide is 1:4-1:3.
7. The reclaimed oil bio-based plastic mixed rubber sole material according to claim 5, wherein the concentration of the toluene solution in the B2 is 10-15%.
8. The reclaimed oil bio-based plastic mixed rubber sole material according to claim 5, wherein the concentration of the ethanol solution in the B3 is 6-8%, and the dosage of the gamma-aminopropyl triethoxysilane is 0.3-0.5% of the total mass.
9. The reclaimed oil bio-based plastic mixed rubber sole material according to claim 5, wherein the isocyanate crosslinking agent in the B4 is toluene diisocyanate and the amount is 1-2% of the total mass, wherein the drying temperature is 80-90 ℃ and the drying time is 3-5 hours.
10. The preparation method of the reclaimed oil bio-based plastic mixed rubber sole material is characterized by comprising the following steps of:
s1, drying the reclaimed oil bio-based plastic under the conditions of constant temperature and constant humidity to remove water contained in the reclaimed oil bio-based plastic;
s2, adding the dried reclaimed oil bio-based plastic and the smoke rubber into an internal mixer or an open mill, setting the rotation speed of the internal mixer to be 30-50 r/min, setting the rotation speed of a roller of the open mill to be 10-15 r/min, controlling the mixing temperature to be 80-100 ℃, and firstly carrying out preliminary mixing for 5-10 min to uniformly mix the reclaimed oil bio-based plastic and the smoke rubber to form a continuous matrix phase;
S3, adding 10-15 parts of modified mixed reinforcing filler and calcium powder into the matrix, and continuously mixing for 10-15 minutes;
s4, sequentially adding dicumyl oxide, zinc oxide, stearic acid, octylated diphenylamine and an antibacterial mildew-proof filler, mixing for 10-15 minutes, wherein the fully dispersed auxiliary agent is ensured in the mixing process, the rotating speed of an internal mixer is maintained at 60-80 r/min, the temperature is 120-140 ℃, the rotating speed of a roller of an open mill is 20-25 r/min, and uniform mixed rubber is obtained after mixing is completed;
S5, preforming the mixed rubber material according to the shape and size requirements of the sole, putting the preformed sole into a vulcanizing machine, setting the vulcanizing temperature to be 150-180 ℃, setting the vulcanizing pressure to be 10-15MPa, and setting the vulcanizing time to be 10-30 minutes;
and S6, taking out the sole from the vulcanizing machine after vulcanization is completed, and performing demolding operation.
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