CN114085538A - High-temperature-resistant natural rubber material and preparation method thereof - Google Patents
High-temperature-resistant natural rubber material and preparation method thereof Download PDFInfo
- Publication number
- CN114085538A CN114085538A CN202111451191.XA CN202111451191A CN114085538A CN 114085538 A CN114085538 A CN 114085538A CN 202111451191 A CN202111451191 A CN 202111451191A CN 114085538 A CN114085538 A CN 114085538A
- Authority
- CN
- China
- Prior art keywords
- natural rubber
- temperature
- mixture
- parts
- prepare
- 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
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a high-temperature-resistant natural rubber material and a preparation method thereof, wherein the high-temperature-resistant natural rubber material comprises the following raw materials in parts by weight: 55-75 parts of modified natural rubber, 15-20 parts of zinc-calcium composite heat stabilizer, 15-25 parts of composite filler, 2-5 parts of anti-aging agent and 6-10 parts of cross-linking agent; firstly, adding modified natural rubber, composite filler, zinc-calcium composite heat stabilizer and anti-aging agent into a high-speed mixer, and stirring at a constant speed for 30min to prepare a mixture; secondly, extruding and molding the mixture and the cross-linking agent at the temperature of 200-220 ℃, and then transferring the mixture and the cross-linking agent into a vulcanizing machine to prepare the high-temperature-resistant natural rubber material; the processed natural rubber is mixed with polyethylene glycol monomethyl ether carboxylic acid, and the polyethylene glycol monomethyl ether carboxylic acid is grafted on the natural rubber through ring-opening esterification reaction to prepare the modified natural rubber which has excellent mechanical properties.
Description
Technical Field
The invention belongs to the technical field of rubber materials, and particularly relates to a high-temperature-resistant natural rubber material and a preparation method thereof.
Background
Natural Rubber (NR) is a natural high molecular compound containing cis-1, 4-polyisoprene as a main component, 91% to 94% of which is rubber hydrocarbon (cis-1, 4-polyisoprene), and the balance of which is non-rubber substances such as protein, fatty acid, ash, saccharides and the like; natural rubber is the most widely used rubber; rubber generates two changes under the action of high temperature or thermal oxygen, namely physical change and chemical change, no matter under the action of pure heat or thermal oxygen, the main chain of a polymer can be broken, a cross-linked network can be damaged, or further cross-linking can be generated, and then hardening and embrittlement of the rubber can be generated, the capability of the rubber for keeping the original physical properties under the action of long-time thermal aging is generally called heat resistance, the requirement on the high temperature resistance of the rubber in various fields is higher, and the common natural rubber can not meet the requirement on high temperature resistance.
The Chinese patent CN104341613A discloses a high-temperature-resistant oil-resistant rubber composition and a preparation method thereof, wherein the composition comprises the following components in parts by weight: 100 parts of natural rubber, 30 parts of tetrafluoroethylene-propylene rubber, 16 parts of ethylene propylene diene monomer, 2 parts of benzoyl peroxide, 12 parts of dibutyl phthalate, 5 parts of anti-aging agent NBC, 6 parts of zinc oxide, 33 parts of calcium carbonate, 2.1 parts of phenol formaldehyde and 3.6 parts of epoxidized soybean oil.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a high-temperature-resistant natural rubber material and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a high-temperature-resistant natural rubber material comprises the following raw materials in parts by weight: 55-75 parts of modified natural rubber, 15-20 parts of zinc-calcium composite heat stabilizer, 15-25 parts of composite filler, 2-5 parts of anti-aging agent and 6-10 parts of cross-linking agent;
the high-temperature-resistant natural rubber material is prepared by the following method:
firstly, adding modified natural rubber, composite filler, zinc-calcium composite heat stabilizer and anti-aging agent into a high-speed mixer, and uniformly stirring for 30min at the rotating speed of 500-1000r/min to prepare a mixture;
and secondly, adding the mixture and the cross-linking agent prepared in the first step into a double-screw extruder, extruding and molding at the temperature of 200-220 ℃, transferring the mixture into a vulcanizing machine, respectively preserving heat for 2h at the temperature of 80-90 ℃, then heating to the temperature of 100-140 ℃, preserving heat for 2h, then heating to the temperature of 120-130 ℃, preserving heat for 0.5h, finally heating to the temperature of 130-140 ℃, preserving heat for 10h, and preparing the high-temperature resistant natural rubber material.
Further, the anti-aging agent is an anti-aging agent 445, and the crosslinking agent is dicumyl peroxide.
Further, the modified natural rubber is prepared by the following method:
step S1, adding natural rubber into deionized water according to the weight ratio of 3: 10, adding a stabilizer A20 while stirring, stirring at a constant speed, reacting for 2 hours, slowly dripping formic acid and aqueous hydrogen peroxide solution with the mass fraction of 10 percent, heating to 45-50 ℃, stirring at constant speed at the temperature, reacting for 48h, transferring to a cold water bath after the reaction is finished, cooling to 25-30 ℃, dropwise adding ammonia water with the mass fraction of 10% to adjust the pH until the pH is 8-9, adding into an open mill for plastication for 30 times, placing into a tetrahydrofuran solvent after the plastication is finished, stirring at 150-, drying at 50-60 deg.C for 12 hr to obtain treated natural rubber, wherein the weight ratio of natural rubber, formic acid and hydrogen peroxide is 1: 5: 0.2-0.5;
and S2, adding the treated natural rubber obtained in the step S1 into dimethylformamide, uniformly stirring until the system is uniform, adding polyethylene glycol monomethyl ether carboxylic acid, introducing nitrogen to discharge air, transferring to a 100-plus-120 ℃ oil bath kettle, uniformly stirring for 8 hours at a rotation speed of 200r/min to obtain a mixed solution, removing excess solvent by rotary evaporation, pouring into a polytetrafluoroethylene mold, volatilizing for 10 hours, transferring to a vacuum drying box, drying for 10 hours under the conditions that the temperature is 80 ℃ and the vacuum degree is-0.10 MPa to obtain a sample, extracting the sample for 24 hours by using methanol, and drying to obtain modified natural rubber, wherein the weight ratio of the natural rubber to the polyethylene glycol monomethyl ether carboxylic acid is controlled to be 1: 3-5.
Mixing natural rubber with formic acid and aqueous hydrogen peroxide in step S1, reacting the formic acid with the aqueous hydrogen peroxide to generate peroxyformic acid, reacting the natural rubber with the peroxyformic acid, epoxidizing and modifying carbon-carbon double bonds on the natural rubber to prepare epoxidized natural rubber, plasticating and purifying to prepare the treated natural rubber, wherein the rubber has epoxy groups and can generate dipole, hydrogen bond and other effects with the surface of a filler so as to improve the interface acting force, a large number of carbon-carbon double bonds are reserved and can be compatible with other rubbers, mixing the treated natural rubber with polyethylene glycol monomethyl ether carboxylic acid in step S12, grafting the polyethylene glycol monomethyl ether carboxylic acid on the natural rubber through ring-opening esterification reaction to prepare the modified natural rubber, and the modified natural rubber has excellent mechanical properties.
Further, the composite filler is prepared by the following method:
step S11, uniformly mixing montmorillonite, urea and ethanol according to the weight ratio of 3: 4-5: 1, transferring the mixture into a three-neck flask, heating in a water bath at 45-55 ℃, stirring for 2-3 hours at the rotating speed of 140r/min to prepare mixed slurry, performing suction filtration, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, drying, and grinding to prepare modified montmorillonite;
step S12, adding calcium carbonate into the nano titanium sol, stirring at a constant speed for 2h to prepare a mixture, drying the mixture at 100 ℃ to prepare gel, transferring the gel into a muffle furnace to calcine at the temperature of 450-500 ℃ for 3h to prepare filler particles, adding the filler particles into an aluminate coupling agent to treat for 3-5min, then transferring into a mixer, adding a composite foaming agent to stir at the rotating speed of 400-450r/min for 30min, finally adding low-density polyethylene to stir at a constant speed for 10min, discharging, adding into a double-screw extruder, adding modified montmorillonite, plasticizing, mixing and extruding the mixture by a double-screw extruder to prepare the composite filler, wherein the weight ratio of the calcium carbonate to the nano titanium sol is controlled to be 0.8-1: 1, and the weight ratio of the filler particles, the aluminate coupling agent, the composite foaming agent, the low-density polyethylene and the modified montmorillonite is 1: 0.5-0.8: 0.05-0.08: 15-20: 0.8-1.
In step S11, montmorillonite, urea and ethanol are mixed uniformly according to the weight ratio of 3: 4-5: 1, intercalation modification is carried out on the montmorillonite, urea is used as an intercalation agent, on one hand, the interlayer spacing of the montmorillonite can be increased, space is provided for other molecules to enter the montmorillonite, calcium carbonate is added into the nano titanium sol in the step S12, the filler particles are prepared by mixing and calcining, the filler particles are calcium carbonate loaded titanium dioxide, then the filler particles, modified montmorillonite, a composite foaming agent and the like are mixed and plasticized and extruded with low-density polyethylene to prepare the composite filler, in the composite filler, a plurality of fillers are synergistically dispersed in polyethylene, filler particles and modified montmorillonite can enhance the bonding force with an organic phase interface, the rubber absorbs tensile stress during stretching, improves the toughness and endows the finally prepared rubber with excellent tensile resistance.
Further, the composite foaming agent is prepared by mixing azodicarbonamide, dicumyl peroxide, stearic acid and liquid paraffin according to the weight ratio of 10: 0.5-0.8: 1-1.5: 2-3.
A preparation method of a high-temperature-resistant natural rubber material comprises the following steps:
firstly, adding modified natural rubber, composite filler, zinc-calcium composite heat stabilizer and anti-aging agent into a high-speed mixer, and uniformly stirring for 30min at the rotating speed of 500-1000r/min to prepare a mixture;
and secondly, adding the mixture and the cross-linking agent prepared in the first step into a double-screw extruder, extruding and molding at the temperature of 200-220 ℃, transferring the mixture into a vulcanizing machine, respectively preserving heat for 2h at the temperature of 80-90 ℃, then heating to the temperature of 100-140 ℃, preserving heat for 2h, then heating to the temperature of 120-130 ℃, preserving heat for 0.5h, finally heating to the temperature of 130-140 ℃, preserving heat for 10h, and preparing the high-temperature resistant natural rubber material.
The invention has the beneficial effects that:
(1) the invention relates to a high-temperature-resistant natural rubber material, which is prepared by modifying natural rubber, composite filler and other raw materials, and can improve the high-temperature resistance of the modified natural rubber by adding a zinc-calcium composite heat stabilizer, wherein the modified natural rubber is prepared by mixing the natural rubber with formic acid and aqueous hydrogen peroxide in step S1, the formic acid reacts with the aqueous hydrogen peroxide to generate peroxyformic acid, the natural rubber reacts with the peroxyformic acid, carbon-carbon double bonds on the natural rubber are epoxidized and modified to prepare epoxidized natural rubber, and then plasticating and purifying to prepare the treated natural rubber, wherein the rubber has epoxy groups, can generate dipole, hydrogen bond and other effects with the surface of the filler to further improve the interface acting force, retains a large amount of carbon-carbon double bonds, can be compatible with other rubbers, and is prepared by mixing the treated natural rubber with polyethylene glycol monomethyl ether carboxylic acid in step S12, grafting polyethylene glycol monomethyl ether carboxylic acid on natural rubber through ring-opening esterification reaction to prepare the modified natural rubber, wherein the modified natural rubber has excellent mechanical properties.
(2) In the preparation process of the composite filler, in the step S11, montmorillonite, urea and ethanol are uniformly mixed according to the weight ratio of 3: 4-5: 1, intercalation modification is carried out on the montmorillonite, urea is used as an intercalation agent, on one hand, the interlayer spacing of the montmorillonite can be increased, space is provided for other molecules to enter the montmorillonite, calcium carbonate is added into the nano titanium sol in the step S12, the filler particles are prepared by mixing and calcining, the filler particles are calcium carbonate loaded titanium dioxide, then the filler particles, modified montmorillonite, a composite foaming agent and the like are mixed and plasticized and extruded with low-density polyethylene to prepare the composite filler, in the composite filler, a plurality of fillers are synergistically dispersed in polyethylene, filler particles and modified montmorillonite can enhance the bonding force with an organic phase interface, the rubber absorbs tensile stress during stretching, improves the toughness and endows the finally prepared rubber with excellent tensile resistance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A high-temperature-resistant natural rubber material comprises the following raw materials in parts by weight: 55 parts of modified natural rubber, 15 parts of a zinc-calcium composite heat stabilizer, 15 parts of a composite filler, 2 parts of an anti-aging agent 445 and 6 parts of dicumyl peroxide;
the high-temperature-resistant natural rubber material is prepared by the following method:
firstly, adding modified natural rubber, composite filler, zinc-calcium composite heat stabilizer and anti-aging agent 445 into a high-speed mixer, and uniformly stirring at a rotating speed of 500r/min for 30min to prepare a mixture;
and secondly, adding the mixture prepared in the first step and dicumyl peroxide into a double-screw extruder, extruding and molding at 200 ℃, transferring the mixture into a vulcanizing machine, respectively preserving heat at 80 ℃ for 2 hours, then heating to 100 ℃, preserving heat for 2 hours, then heating to 120 ℃, preserving heat for 0.5 hour, finally heating to 130 ℃, and preserving heat for 10 hours to prepare the high-temperature-resistant natural rubber material.
The modified natural rubber is prepared by the following method:
step S1, adding natural rubber into deionized water according to the weight ratio of 3: 10, adding a stabilizer A20 while stirring, stirring at a constant speed, reacting for 2 hours, slowly dropwise adding formic acid and aqueous hydrogen peroxide with the mass fraction of 10%, heating to 45 ℃, stirring at a constant speed at the temperature, reacting for 48 hours, transferring to a cold water bath after the reaction is finished, cooling to 25 ℃, dropwise adding aqueous ammonia with the mass fraction of 10% to adjust the pH until the pH is 8, then adding to an open mill for plastication, carrying out thin passing for 30 times, placing in a tetrahydrofuran solvent after the plastication, stirring at a constant speed of 150r/min until a uniform solution is formed, then placing in methanol for precipitation, washing the precipitate with absolute ethyl alcohol for three times, drying at 50 ℃ for 12 hours to obtain the treated natural rubber, and controlling the weight ratio of the natural rubber, the formic acid and the hydrogen peroxide to be 1: 5: 0.2;
and S2, adding the treated natural rubber obtained in the step S1 into dimethylformamide, uniformly stirring until the system is uniform, adding polyethylene glycol monomethyl ether carboxylic acid, introducing nitrogen to discharge air, transferring to a 100 ℃ oil bath kettle, uniformly stirring for 8 hours at a rotating speed of 150r/min to obtain a mixed solution, removing excess solvent by rotary evaporation, pouring into a polytetrafluoroethylene mold, volatilizing for 10 hours, transferring to a vacuum drying oven, drying for 10 hours at a temperature of 80 ℃ and a vacuum degree of-0.10 MPa to obtain a sample, extracting the sample with methanol for 24 hours, and drying to obtain modified natural rubber, wherein the weight ratio of the natural rubber to the polyethylene glycol monomethyl ether carboxylic acid is controlled to be 1: 3.
The composite filler is prepared by the following method:
step S11, uniformly mixing montmorillonite, urea and ethanol according to the weight ratio of 3: 4: 1, transferring the mixture into a three-neck flask, heating the mixture in a water bath at 45 ℃ and stirring the mixture for 2 hours at the rotating speed of 140r/min to prepare mixed slurry, performing suction filtration, washing the mixed slurry with deionized water for three times, washing the mixed slurry with absolute ethyl alcohol for three times, drying and grinding the washed mixed slurry to prepare modified montmorillonite;
step S12, adding calcium carbonate into the nano titanium sol, stirring at a constant speed for 2 hours to obtain a mixture, drying the mixture at 100 ℃ to obtain gel, transferring the gel into a muffle furnace, calcining at 450 ℃ for 3 hours to obtain filler particles, adding the filler particles into an aluminate coupling agent, treating for 3 minutes, transferring into a mixer, adding a composite foaming agent, stirring at a rotating speed of 400r/min for 30 minutes, finally adding low-density polyethylene, stirring at a constant speed for 10 minutes, discharging, adding into a double-screw extruder, adding modified montmorillonite, plasticizing, mixing and extruding through the double-screw extruder to obtain the composite filler, wherein the weight ratio of the calcium carbonate to the nano titanium sol is controlled to be 0.8: 1, and the weight ratio of the filler particles, the aluminate coupling agent, the composite foaming agent, the low-density polyethylene and the modified montmorillonite is controlled to be 1: 0.5: 0.05: 15: 0.8.
The composite foaming agent is prepared by mixing azodicarbonamide, dicumyl peroxide, stearic acid and liquid paraffin according to the weight ratio of 10: 0.5: 1: 2.
Example 2
A high-temperature-resistant natural rubber material comprises the following raw materials in parts by weight: 60 parts of modified natural rubber, 16 parts of zinc-calcium composite heat stabilizer, 18 parts of composite filler, 3 parts of anti-aging agent 445 and 8 parts of dicumyl peroxide;
the high-temperature-resistant natural rubber material is prepared by the following method:
firstly, adding modified natural rubber, composite filler, zinc-calcium composite heat stabilizer and anti-aging agent 445 into a high-speed mixer, and uniformly stirring at a rotating speed of 500r/min for 30min to prepare a mixture;
and secondly, adding the mixture prepared in the first step and dicumyl peroxide into a double-screw extruder, extruding and molding at 200 ℃, transferring the mixture into a vulcanizing machine, respectively preserving heat at 80 ℃ for 2 hours, then heating to 100 ℃, preserving heat for 2 hours, then heating to 120 ℃, preserving heat for 0.5 hour, finally heating to 130 ℃, and preserving heat for 10 hours to prepare the high-temperature-resistant natural rubber material.
The modified natural rubber is prepared by the following method:
step S1, adding natural rubber into deionized water according to the weight ratio of 3: 10, adding a stabilizer A20 while stirring, stirring at a constant speed, reacting for 2 hours, slowly dropwise adding formic acid and aqueous hydrogen peroxide with the mass fraction of 10%, heating to 45 ℃, stirring at a constant speed at the temperature, reacting for 48 hours, transferring to a cold water bath after the reaction is finished, cooling to 25 ℃, dropwise adding aqueous ammonia with the mass fraction of 10% to adjust the pH until the pH is 8, then adding to an open mill for plastication, carrying out thin passing for 30 times, placing in a tetrahydrofuran solvent after the plastication, stirring at a constant speed of 150r/min until a uniform solution is formed, then placing in methanol for precipitation, washing the precipitate with absolute ethyl alcohol for three times, drying at 50 ℃ for 12 hours to obtain the treated natural rubber, and controlling the weight ratio of the natural rubber, the formic acid and the hydrogen peroxide to be 1: 5: 0.2;
and S2, adding the treated natural rubber obtained in the step S1 into dimethylformamide, uniformly stirring until the system is uniform, adding polyethylene glycol monomethyl ether carboxylic acid, introducing nitrogen to discharge air, transferring to a 100 ℃ oil bath kettle, uniformly stirring for 8 hours at a rotating speed of 150r/min to obtain a mixed solution, removing excess solvent by rotary evaporation, pouring into a polytetrafluoroethylene mold, volatilizing for 10 hours, transferring to a vacuum drying oven, drying for 10 hours at a temperature of 80 ℃ and a vacuum degree of-0.10 MPa to obtain a sample, extracting the sample with methanol for 24 hours, and drying to obtain modified natural rubber, wherein the weight ratio of the natural rubber to the polyethylene glycol monomethyl ether carboxylic acid is controlled to be 1: 3.
The composite filler is prepared by the following method:
step S11, uniformly mixing montmorillonite, urea and ethanol according to the weight ratio of 3: 4: 1, transferring the mixture into a three-neck flask, heating the mixture in a water bath at 45 ℃ and stirring the mixture for 2 hours at the rotating speed of 140r/min to prepare mixed slurry, performing suction filtration, washing the mixed slurry with deionized water for three times, washing the mixed slurry with absolute ethyl alcohol for three times, drying and grinding the washed mixed slurry to prepare modified montmorillonite;
step S12, adding calcium carbonate into the nano titanium sol, stirring at a constant speed for 2 hours to obtain a mixture, drying the mixture at 100 ℃ to obtain gel, transferring the gel into a muffle furnace, calcining at 450 ℃ for 3 hours to obtain filler particles, adding the filler particles into an aluminate coupling agent, treating for 3 minutes, transferring into a mixer, adding a composite foaming agent, stirring at a rotating speed of 400r/min for 30 minutes, finally adding low-density polyethylene, stirring at a constant speed for 10 minutes, discharging, adding into a double-screw extruder, adding modified montmorillonite, plasticizing, mixing and extruding through the double-screw extruder to obtain the composite filler, wherein the weight ratio of the calcium carbonate to the nano titanium sol is controlled to be 0.8: 1, and the weight ratio of the filler particles, the aluminate coupling agent, the composite foaming agent, the low-density polyethylene and the modified montmorillonite is controlled to be 1: 0.5: 0.05: 15: 0.8.
The composite foaming agent is prepared by mixing azodicarbonamide, dicumyl peroxide, stearic acid and liquid paraffin according to the weight ratio of 10: 0.5: 1: 2.
Example 3
A high-temperature-resistant natural rubber material comprises the following raw materials in parts by weight: 70 parts of modified natural rubber, 18 parts of zinc-calcium composite heat stabilizer, 22 parts of composite filler, 4 parts of anti-aging agent 445 and 8 parts of dicumyl peroxide;
the high-temperature-resistant natural rubber material is prepared by the following method:
firstly, adding modified natural rubber, composite filler, zinc-calcium composite heat stabilizer and anti-aging agent 445 into a high-speed mixer, and uniformly stirring at a rotating speed of 500r/min for 30min to prepare a mixture;
and secondly, adding the mixture prepared in the first step and dicumyl peroxide into a double-screw extruder, extruding and molding at 200 ℃, transferring the mixture into a vulcanizing machine, respectively preserving heat at 80 ℃ for 2 hours, then heating to 100 ℃, preserving heat for 2 hours, then heating to 120 ℃, preserving heat for 0.5 hour, finally heating to 130 ℃, and preserving heat for 10 hours to prepare the high-temperature-resistant natural rubber material.
The modified natural rubber is prepared by the following method:
step S1, adding natural rubber into deionized water according to the weight ratio of 3: 10, adding a stabilizer A20 while stirring, stirring at a constant speed, reacting for 2 hours, slowly dropwise adding formic acid and aqueous hydrogen peroxide with the mass fraction of 10%, heating to 45 ℃, stirring at a constant speed at the temperature, reacting for 48 hours, transferring to a cold water bath after the reaction is finished, cooling to 25 ℃, dropwise adding aqueous ammonia with the mass fraction of 10% to adjust the pH until the pH is 8, then adding to an open mill for plastication, carrying out thin passing for 30 times, placing in a tetrahydrofuran solvent after the plastication, stirring at a constant speed of 150r/min until a uniform solution is formed, then placing in methanol for precipitation, washing the precipitate with absolute ethyl alcohol for three times, drying at 50 ℃ for 12 hours to obtain the treated natural rubber, and controlling the weight ratio of the natural rubber, the formic acid and the hydrogen peroxide to be 1: 5: 0.2;
and S2, adding the treated natural rubber obtained in the step S1 into dimethylformamide, uniformly stirring until the system is uniform, adding polyethylene glycol monomethyl ether carboxylic acid, introducing nitrogen to discharge air, transferring to a 100 ℃ oil bath kettle, uniformly stirring for 8 hours at a rotating speed of 150r/min to obtain a mixed solution, removing excess solvent by rotary evaporation, pouring into a polytetrafluoroethylene mold, volatilizing for 10 hours, transferring to a vacuum drying oven, drying for 10 hours at a temperature of 80 ℃ and a vacuum degree of-0.10 MPa to obtain a sample, extracting the sample with methanol for 24 hours, and drying to obtain modified natural rubber, wherein the weight ratio of the natural rubber to the polyethylene glycol monomethyl ether carboxylic acid is controlled to be 1: 3.
The composite filler is prepared by the following method:
step S11, uniformly mixing montmorillonite, urea and ethanol according to the weight ratio of 3: 4: 1, transferring the mixture into a three-neck flask, heating the mixture in a water bath at 45 ℃ and stirring the mixture for 2 hours at the rotating speed of 140r/min to prepare mixed slurry, performing suction filtration, washing the mixed slurry with deionized water for three times, washing the mixed slurry with absolute ethyl alcohol for three times, drying and grinding the washed mixed slurry to prepare modified montmorillonite;
step S12, adding calcium carbonate into the nano titanium sol, stirring at a constant speed for 2 hours to obtain a mixture, drying the mixture at 100 ℃ to obtain gel, transferring the gel into a muffle furnace, calcining at 450 ℃ for 3 hours to obtain filler particles, adding the filler particles into an aluminate coupling agent, treating for 3 minutes, transferring into a mixer, adding a composite foaming agent, stirring at a rotating speed of 400r/min for 30 minutes, finally adding low-density polyethylene, stirring at a constant speed for 10 minutes, discharging, adding into a double-screw extruder, adding modified montmorillonite, plasticizing, mixing and extruding through the double-screw extruder to obtain the composite filler, wherein the weight ratio of the calcium carbonate to the nano titanium sol is controlled to be 0.8: 1, and the weight ratio of the filler particles, the aluminate coupling agent, the composite foaming agent, the low-density polyethylene and the modified montmorillonite is controlled to be 1: 0.5: 0.05: 15: 0.8.
The composite foaming agent is prepared by mixing azodicarbonamide, dicumyl peroxide, stearic acid and liquid paraffin according to the weight ratio of 10: 0.5: 1: 2.
Example 4
A high-temperature-resistant natural rubber material comprises the following raw materials in parts by weight: 75 parts of modified natural rubber, 20 parts of zinc-calcium composite heat stabilizer, 25 parts of composite filler, 5 parts of anti-aging agent 445 and 10 parts of dicumyl peroxide;
the high-temperature-resistant natural rubber material is prepared by the following method:
firstly, adding modified natural rubber, composite filler, zinc-calcium composite heat stabilizer and anti-aging agent 445 into a high-speed mixer, and uniformly stirring at a rotating speed of 500r/min for 30min to prepare a mixture;
and secondly, adding the mixture prepared in the first step and dicumyl peroxide into a double-screw extruder, extruding and molding at 200 ℃, transferring the mixture into a vulcanizing machine, respectively preserving heat at 80 ℃ for 2 hours, then heating to 100 ℃, preserving heat for 2 hours, then heating to 120 ℃, preserving heat for 0.5 hour, finally heating to 130 ℃, and preserving heat for 10 hours to prepare the high-temperature-resistant natural rubber material.
The modified natural rubber is prepared by the following method:
step S1, adding natural rubber into deionized water according to the weight ratio of 3: 10, adding a stabilizer A20 while stirring, stirring at a constant speed, reacting for 2 hours, slowly dropwise adding formic acid and aqueous hydrogen peroxide with the mass fraction of 10%, heating to 45 ℃, stirring at a constant speed at the temperature, reacting for 48 hours, transferring to a cold water bath after the reaction is finished, cooling to 25 ℃, dropwise adding aqueous ammonia with the mass fraction of 10% to adjust the pH until the pH is 8, then adding to an open mill for plastication, carrying out thin passing for 30 times, placing in a tetrahydrofuran solvent after the plastication, stirring at a constant speed of 150r/min until a uniform solution is formed, then placing in methanol for precipitation, washing the precipitate with absolute ethyl alcohol for three times, drying at 50 ℃ for 12 hours to obtain the treated natural rubber, and controlling the weight ratio of the natural rubber, the formic acid and the hydrogen peroxide to be 1: 5: 0.2;
and S2, adding the treated natural rubber obtained in the step S1 into dimethylformamide, uniformly stirring until the system is uniform, adding polyethylene glycol monomethyl ether carboxylic acid, introducing nitrogen to discharge air, transferring to a 100 ℃ oil bath kettle, uniformly stirring for 8 hours at a rotating speed of 150r/min to obtain a mixed solution, removing excess solvent by rotary evaporation, pouring into a polytetrafluoroethylene mold, volatilizing for 10 hours, transferring to a vacuum drying oven, drying for 10 hours at a temperature of 80 ℃ and a vacuum degree of-0.10 MPa to obtain a sample, extracting the sample with methanol for 24 hours, and drying to obtain modified natural rubber, wherein the weight ratio of the natural rubber to the polyethylene glycol monomethyl ether carboxylic acid is controlled to be 1: 3.
The composite filler is prepared by the following method:
step S11, uniformly mixing montmorillonite, urea and ethanol according to the weight ratio of 3: 4: 1, transferring the mixture into a three-neck flask, heating the mixture in a water bath at 45 ℃ and stirring the mixture for 2 hours at the rotating speed of 140r/min to prepare mixed slurry, performing suction filtration, washing the mixed slurry with deionized water for three times, washing the mixed slurry with absolute ethyl alcohol for three times, drying and grinding the washed mixed slurry to prepare modified montmorillonite;
step S12, adding calcium carbonate into the nano titanium sol, stirring at a constant speed for 2 hours to obtain a mixture, drying the mixture at 100 ℃ to obtain gel, transferring the gel into a muffle furnace, calcining at 450 ℃ for 3 hours to obtain filler particles, adding the filler particles into an aluminate coupling agent, treating for 3 minutes, transferring into a mixer, adding a composite foaming agent, stirring at a rotating speed of 400r/min for 30 minutes, finally adding low-density polyethylene, stirring at a constant speed for 10 minutes, discharging, adding into a double-screw extruder, adding modified montmorillonite, plasticizing, mixing and extruding through the double-screw extruder to obtain the composite filler, wherein the weight ratio of the calcium carbonate to the nano titanium sol is controlled to be 0.8: 1, and the weight ratio of the filler particles, the aluminate coupling agent, the composite foaming agent, the low-density polyethylene and the modified montmorillonite is controlled to be 1: 0.5: 0.05: 15: 0.8.
The composite foaming agent is prepared by mixing azodicarbonamide, dicumyl peroxide, stearic acid and liquid paraffin according to the weight ratio of 10: 0.5: 1: 2.
Comparative example 1
This comparative example compares to the examples, replacing the modified natural rubber with natural rubber.
Comparative example 2
In comparison with the examples, the composite filler was not added in this comparative example.
Comparative example 3
The comparative example is a high-temperature-resistant natural rubber material in the market.
Mechanical properties were tested by heating examples 1-4 and comparative examples 1-3 at 150 ℃ for 1000 h.
As can be seen from the above table, the tensile strength of examples 1-4 was 16-17MPa, the elongation was 342-348%, and the tensile strength of comparative examples 1-3 was 12-15MPa, the elongation was 260-285%; in the composite filler, a plurality of fillers are synergistically dispersed in polyethylene, filler particles and modified montmorillonite can enhance the bonding force with an organic phase interface, absorb tensile stress during stretching, improve the toughness of the composite filler, and endow the finally prepared rubber with excellent tensile resistance.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (6)
1. The high-temperature-resistant natural rubber material is characterized by comprising the following raw materials in parts by weight: 55-75 parts of modified natural rubber, 15-20 parts of zinc-calcium composite heat stabilizer, 15-25 parts of composite filler, 2-5 parts of anti-aging agent, 6-10 parts of cross-linking agent,
the high-temperature-resistant natural rubber material is prepared by the following method:
firstly, adding modified natural rubber, composite filler, zinc-calcium composite heat stabilizer and anti-aging agent into a high-speed mixer, and uniformly stirring for 30min at the rotating speed of 500-1000r/min to prepare a mixture;
and secondly, adding the mixture and the cross-linking agent prepared in the first step into a double-screw extruder, extruding and molding at the temperature of 200-220 ℃, transferring the mixture into a vulcanizing machine, respectively preserving heat for 2h at the temperature of 80-90 ℃, then heating to the temperature of 100-140 ℃, preserving heat for 2h, then heating to the temperature of 120-130 ℃, preserving heat for 0.5h, finally heating to the temperature of 130-140 ℃, preserving heat for 10h, and preparing the high-temperature resistant natural rubber material.
2. The high temperature resistant natural rubber material as defined in claim 1, wherein the antioxidant is antioxidant 445, and the crosslinking agent is dicumyl peroxide.
3. The high-temperature-resistant natural rubber material as claimed in claim 1, wherein the modified natural rubber is prepared by the following method:
step S1, adding natural rubber into deionized water according to the weight ratio of 3: 10, adding a stabilizer A20 while stirring, stirring at a constant speed, reacting for 2 hours, slowly dripping formic acid and aqueous hydrogen peroxide solution with the mass fraction of 10 percent, heating to 45-50 ℃, stirring at constant speed at the temperature, reacting for 48h, transferring to a cold water bath after the reaction is finished, cooling to 25-30 ℃, dropwise adding ammonia water with the mass fraction of 10% to adjust the pH until the pH is 8-9, adding into an open mill for plastication for 30 times, placing into a tetrahydrofuran solvent after the plastication is finished, stirring at 150-, drying at 50-60 deg.C for 12 hr to obtain treated natural rubber, wherein the weight ratio of natural rubber, formic acid and hydrogen peroxide is 1: 5: 0.2-0.5;
and S2, adding the treated natural rubber obtained in the step S1 into dimethylformamide, uniformly stirring until the system is uniform, adding polyethylene glycol monomethyl ether carboxylic acid, introducing nitrogen to discharge air, transferring to a 100-plus-120 ℃ oil bath kettle, uniformly stirring for 8 hours at a rotation speed of 200r/min to obtain a mixed solution, removing excess solvent by rotary evaporation, pouring into a polytetrafluoroethylene mold, volatilizing for 10 hours, transferring to a vacuum drying box, drying for 10 hours under the conditions that the temperature is 80 ℃ and the vacuum degree is-0.10 MPa to obtain a sample, extracting the sample for 24 hours by using methanol, and drying to obtain modified natural rubber, wherein the weight ratio of the natural rubber to the polyethylene glycol monomethyl ether carboxylic acid is controlled to be 1: 3-5.
4. The high-temperature-resistant natural rubber material as claimed in claim 1, wherein the composite filler is prepared by the following method:
step S11, uniformly mixing montmorillonite, urea and ethanol according to the weight ratio of 3: 4-5: 1, transferring the mixture into a three-neck flask, heating in a water bath at 45-55 ℃, stirring for 2-3 hours at the rotating speed of 140r/min to prepare mixed slurry, performing suction filtration, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, drying, and grinding to prepare modified montmorillonite;
step S12, adding calcium carbonate into the nano titanium sol, stirring at a constant speed for 2h to prepare a mixture, drying the mixture at 100 ℃ to prepare gel, transferring the gel into a muffle furnace to calcine at the temperature of 450-500 ℃ for 3h to prepare filler particles, adding the filler particles into an aluminate coupling agent to treat for 3-5min, then transferring into a mixer, adding a composite foaming agent to stir at the rotating speed of 400-450r/min for 30min, finally adding low-density polyethylene to stir at a constant speed for 10min, discharging, adding into a double-screw extruder, adding modified montmorillonite, plasticizing, mixing and extruding the mixture by a double-screw extruder to prepare the composite filler, wherein the weight ratio of the calcium carbonate to the nano titanium sol is controlled to be 0.8-1: 1, and the weight ratio of the filler particles, the aluminate coupling agent, the composite foaming agent, the low-density polyethylene and the modified montmorillonite is 1: 0.5-0.8: 0.05-0.08: 15-20: 0.8-1.
5. The high-temperature-resistant natural rubber material as claimed in claim 4, wherein the composite foaming agent is prepared by mixing azodicarbonamide, dicumyl peroxide, stearic acid and liquid paraffin according to a weight ratio of 10: 0.5-0.8: 1-1.5: 2-3.
6. The method for preparing the high-temperature-resistant natural rubber material according to claim 1, comprising the following steps of:
firstly, adding modified natural rubber, composite filler, zinc-calcium composite heat stabilizer and anti-aging agent into a high-speed mixer, and uniformly stirring for 30min at the rotating speed of 500-1000r/min to prepare a mixture;
and secondly, adding the mixture and the cross-linking agent prepared in the first step into a double-screw extruder, extruding and molding at the temperature of 200-220 ℃, transferring the mixture into a vulcanizing machine, respectively preserving heat for 2h at the temperature of 80-90 ℃, then heating to the temperature of 100-140 ℃, preserving heat for 2h, then heating to the temperature of 120-130 ℃, preserving heat for 0.5h, finally heating to the temperature of 130-140 ℃, preserving heat for 10h, and preparing the high-temperature resistant natural rubber material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111451191.XA CN114085538A (en) | 2021-12-01 | 2021-12-01 | High-temperature-resistant natural rubber material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111451191.XA CN114085538A (en) | 2021-12-01 | 2021-12-01 | High-temperature-resistant natural rubber material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114085538A true CN114085538A (en) | 2022-02-25 |
Family
ID=80305993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111451191.XA Pending CN114085538A (en) | 2021-12-01 | 2021-12-01 | High-temperature-resistant natural rubber material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114085538A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115505054A (en) * | 2022-09-21 | 2022-12-23 | 江苏麒祥高新材料有限公司 | Modified epoxidized rubber and preparation method and application thereof |
-
2021
- 2021-12-01 CN CN202111451191.XA patent/CN114085538A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115505054A (en) * | 2022-09-21 | 2022-12-23 | 江苏麒祥高新材料有限公司 | Modified epoxidized rubber and preparation method and application thereof |
| WO2024060640A1 (en) * | 2022-09-21 | 2024-03-28 | 江苏麒祥高新材料有限公司 | Modified epoxidized rubber, preparation method therefor, and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108822468B (en) | High melt strength grafted polypropylene prepared step by step and preparation method and application thereof | |
| CN107383475A (en) | A kind of lignin/nitile-butadiene rubber composite material and preparation method thereof | |
| CN116217813A (en) | Modified ethylene propylene diene monomer and ethylene propylene diene monomer composite elastomer and preparation method thereof | |
| CN112375262A (en) | Wear-resistant sole material and preparation method thereof | |
| CN114085538A (en) | High-temperature-resistant natural rubber material and preparation method thereof | |
| CN113234291B (en) | Polystyrene carbon black master batch and preparation method thereof | |
| CN116463091B (en) | Double-component weather-resistant epoxy adhesive and preparation method thereof | |
| CN111533980A (en) | Preparation method of stretch-resistant polyethylene film | |
| CN116285284A (en) | CO (carbon monoxide) 2 Composition of base biodegradable copolymer, preparation method and application thereof | |
| CN110256761A (en) | A kind of emulation plant and preparation method thereof | |
| CN110437547A (en) | A kind of TPV material and preparation method thereof with excellent buckling performance | |
| CN115772080A (en) | Preparation method and application of acrylic acid modified sorbitol water tree inhibitor | |
| CN113201211A (en) | Composite dynamic cross-linked polylactic acid/natural rubber/starch elastomer and preparation method thereof | |
| CN112608550A (en) | Strippable semiconductive shielding irradiation material and preparation method thereof | |
| CN112724517A (en) | High-wear-resistance rubber pipe based on modified PP (polypropylene) resin and preparation method thereof | |
| CN114907681B (en) | High-strength polycarbonate film and preparation method thereof | |
| CN115044076B (en) | Surface-modified milled fiber, preparation method thereof, high-toughness modified epoxy resin prepared from surface-modified milled fiber and preparation method of high-toughness modified epoxy resin | |
| CN116178669B (en) | High-toughness reaction injection molding material and application thereof | |
| CN115449212B (en) | Process for preparing biodegradable polyurethane elastomer | |
| CN114854180B (en) | Thermoplastic cellulose/PBAT composite film and preparation method thereof | |
| KR102644448B1 (en) | Manufacturing method of epdm with polar group amd epdm with polar group using the same | |
| WO2023123076A1 (en) | Anti-deformation plastic and preparation process therefor | |
| CN116396544A (en) | Biomass melanin particle composite hydrogenated nitrile rubber and preparation method thereof | |
| CN113265132A (en) | Composite dynamic cross-linked PLA/PBS/NR/starch elastomer and preparation method thereof | |
| CN117866306A (en) | Tough natural epoxy rubber elastomer 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220225 |
|
| RJ01 | Rejection of invention patent application after publication |