CN116082849B - Synthesis process and application of ethylene propylene diene monomer modified EVA material - Google Patents
Synthesis process and application of ethylene propylene diene monomer modified EVA material Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to the technical field of EVA materials, and discloses a synthesis process and application of an ethylene propylene diene monomer modified EVA material, wherein acrylonitrile is utilized to carry out grafting reaction on ethylene propylene diene monomer to obtain cyano ethylene propylene diene monomer, and the cyano ethylene propylene diene monomer is subjected to RaneyNi catalytic ammonification to obtain amino ethylene propylene diene monomer. The carbon nano tube is oxidized by concentrated sulfuric acid and concentrated nitric acid to obtain an acidified carbon nano tube, the generated hydroxyl is then subjected to ring opening with glutaric anhydride to obtain a carboxylated carbon nano tube, so that the carboxyl content on the surface of the carbon nano tube is improved, the carboxylated carbon nano tube is reacted with thionyl chloride to obtain an acyl chlorinated carbon nano tube, the acyl chlorinated carbon nano tube and the aminated ethylene propylene diene monomer are catalyzed by triethylamine to obtain carbon nano tube grafted ethylene propylene diene monomer, and the carbon nano tube grafted ethylene propylene diene monomer is used as a reinforcing agent to be blended with EVA to obtain an ethylene propylene diene monomer modified EVA material, so that the modified ethylene propylene diene monomer has wide application prospect in wear-resistant materials such as soles.
Description
Technical Field
The invention relates to the technical field of EVA materials, in particular to a synthesis process and application of an ethylene propylene diene monomer modified EVA material.
Background
EVA is a copolymer of ethylene and acetic acid, has excellent flexibility, weather resistance, chemical resistance and other excellent processing performances, and is applied to the shoemaking industry, such as photovoltaic materials, solar cell adhesives, greenhouse films, packaging molds, hot melt adhesives, wires and cables and other fields. Ethylene propylene diene monomer is a terpolymer of ethylene, propylene and non-conjugated diene, has excellent aging resistance such as acid and alkali resistance, heat resistance, corrosion resistance, electrical insulation property and the like, and can be widely used in the fields of automobile parts, waterproof materials for buildings, wire and cable jackets, heat-resistant rubber tubes and the like. The patent with the publication number of CN115746438A discloses an EVA composite foaming sole containing itaconate rubber and a preparation method thereof, which lead the prepared EVA composite foaming sole to have higher bio-based content, low carbon and environmental protection, small density, high rebound rate, small dimensional shrinkage and good anti-skid performance, in particular good anti-wet skid performance.
The carbon nano tube is a one-dimensional nano material, has excellent electrical conductivity, thermal conductivity, corrosion resistance and mechanical property, and is often applied to the fields of wear-resistant materials such as high-strength plastics, rubber and the like. For example, patent publication No. CN105670162B discloses a preparation method of a high-toughness antistatic PVC composite sole material, wherein the prepared sole material has lower surface resistivity, better durability of antistatic performance and better toughness. The ethylene propylene diene monomer modified EVA prepared by the invention has the advantages of excellent tensile strength, tearing strength, compression set performance, hardness and the like.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a synthesis process of an ethylene propylene diene monomer modified EVA material, and the prepared ethylene propylene diene monomer modified EVA has the advantages of excellent tensile strength, tearing strength, compression set performance, hardness and the like.
(II) technical scheme
A synthesis process of ethylene propylene diene monomer modified EVA material comprises the following steps:
(1) Synthesis of aminated ethylene propylene diene monomer
Adding cyanated ethylene propylene diene monomer and an activated Raney Ni catalyst into a flask filled with dimethylbenzene at 60-80 ℃ in sequence, controlling the reaction pressure to be 5-7MPa, and stirring and reacting for 60-140min to obtain the amino ethylene propylene diene monomer.
(2) Synthesis of carbon nanotube grafted ethylene propylene diene monomer
And (3) sequentially adding the acyl chloride carbon nano tube, the aminated ethylene propylene diene monomer, the triethylamine and the N, N-dimethylformamide into the flask under the nitrogen atmosphere, carrying out reflux reaction for 20-26h at 70-90 ℃, and cooling to room temperature to obtain the carbon nano tube grafted ethylene propylene diene monomer.
(3) Synthesis of ethylene propylene diene monomer modified EVA material
Adding carbon nanotube grafted ethylene propylene diene monomer, EVA elastomer, hydroxyl silicone oil and vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide into an open mill, mixing for 5-10min, placing the mixed sizing material into the vulcanizing machine at 150-170 ℃ and 8-12MPa for film pressing for 20-30min, placing into an oven at 170-180 ℃ for secondary vulcanization for 4-6h, and cooling to room temperature to obtain the ethylene propylene diene monomer modified EVA material.
Preferably, the mass ratio of the cyanated ethylene propylene diene monomer to the Raney Ni catalyst in the step (1) is 1:0.1-0.2.
Preferably, in the step (2), the mass ratio of the acyl chloride carbon nano tube, the amination ethylene propylene diene monomer and the triethylamine is 1:0.1-0.3:0.1-0.2.
Preferably, in the step (3), the mass ratio of the carbon nanotube grafted ethylene propylene diene monomer, the EVA elastomer, the hydroxyl silicone oil and the vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide is 1:0.1-0.4:0.01-0.05:0.01-0.03.
Preferably, the synthesis process of the cyanated ethylene propylene diene monomer in the step (1) comprises the following steps:
adding ethylene propylene diene monomer into a flask filled with dimethylbenzene at 50-60 ℃ and stirring until the ethylene propylene diene monomer is completely dissolved, and sequentially adding acrylonitrile and azobisisobutyronitrile into the flask at 65-75 ℃ and stirring for reaction for 3-5h, wherein the mass ratio of the ethylene propylene diene monomer to the acrylonitrile to the azobisisobutyronitrile is 1:0.05-0.07:0.005-0.006, acetone precipitation, N-dimethylformamide extraction, vacuum drying to obtain cyano ethylene propylene diene monomer.
Preferably, the synthesis process of the Raney Ni catalyst activated in the step (1) comprises the following steps:
grinding nickel-aluminum alloy with the mass fraction of 40% in a ball mill, adding the ground nickel-aluminum alloy into an aqueous solution containing 17-30% of sodium hydroxide with the mass fraction of 30% at 50-70 ℃ for stirring reaction for 30-60min, and washing with distilled water to obtain the Raney Ni catalyst after activation treatment.
Preferably, the synthesis process of the acyl-chlorinated carbon nanotubes in the step (2) comprises the following steps:
s1, adding the carbon nano tube into concentrated sulfuric acid and concentrated nitric acid solution with the volume ratio of 3:1, heating and refluxing for acidification, and then sequentially adding the acidified carbon nano tube, glutaric anhydride and toluene into a flask at 50-100 ℃, wherein the mass ratio of the acidified carbon nano tube to the glutaric anhydride is 1:3-10, stirring and reacting for 2-5h, and cooling to room temperature to obtain the carboxylated carbon nano tube.
S2, sequentially adding carboxylated carbon nanotubes, thionyl chloride and N, N-dimethylformamide into a flask at the temperature of 70-90 ℃, wherein the mass ratio of the carboxylated carbon nanotubes to the thionyl chloride is 1:1.5-2, stirring uniformly, carrying out reflux reaction for 20-26h, washing with anhydrous tetrahydrofuran, and carrying out vacuum drying to obtain the carbon acyl chloride nanotubes.
(III) beneficial technical effects
The acrylonitrile is used for carrying out grafting reaction on the ethylene propylene diene monomer to obtain the cyano ethylene propylene diene monomer, and the cyano ethylene propylene diene monomer is subjected to RaneyNi catalytic ammonification to obtain the amino ethylene propylene diene monomer. The carbon nano tube is oxidized by concentrated sulfuric acid and concentrated nitric acid to obtain an acidified carbon nano tube, the generated hydroxyl is subjected to ring opening with glutaric anhydride to obtain a carboxylated carbon nano tube, so that the carboxyl content on the surface of the carbon nano tube is improved, the carboxylated carbon nano tube is reacted with thionyl chloride to obtain an acyl chlorinated carbon nano tube, the acyl chlorinated carbon nano tube and the aminated ethylene propylene diene monomer are catalyzed by triethylamine to obtain carbon nano tube grafted ethylene propylene diene monomer, and the carbon nano tube grafted ethylene propylene diene monomer is used as an enhancer to be blended with EVA to obtain the ethylene propylene diene monomer modified EVA material. The carbon nano tube grafted ethylene propylene diene monomer rubber is dispersed in EVA, the compatibility and interaction of the carbon nano tube grafted ethylene propylene diene monomer rubber and the EVA are increased, when the ethylene propylene diene monomer rubber is impacted, a large amount of impact energy can be absorbed by the deformation behavior of shearing yield, the impact energy of crack branching dissipation is low, obvious plastic deformation and holes exist, a 'flake' -shaped appearance is formed, and crack branching is terminated. The ethylene propylene diene monomer modified EVA material has the advantages of excellent tensile strength, tearing strength, compression set performance, hardness and the like, and has wide application prospect in wear-resistant materials such as soles and the like.
Detailed Description
Example 1
(1) Synthesis of cyanated ethylene propylene diene monomer
150g of ethylene propylene diene monomer is added into a flask filled with dimethylbenzene at 60 ℃ and stirred until the ethylene propylene diene monomer is completely dissolved, 8g of acrylonitrile and 0.8g of azodiisobutyronitrile are sequentially added into the flask at 70 ℃ under nitrogen atmosphere and stirred for 3 hours, acetone precipitation, N-dimethylformamide extraction and vacuum drying are carried out, and the cyano ethylene propylene diene monomer is obtained.
(2) Synthesis of activated Raney Ni catalyst
Grinding nickel-aluminum alloy with the mass fraction of 40% in a ball mill, adding the ground nickel-aluminum alloy into an aqueous solution containing 17% of sodium hydroxide at 50 ℃ for stirring reaction for 30min, and washing with distilled water to obtain the Raney Ni catalyst after the activation treatment.
(3) Synthesis of aminated ethylene propylene diene monomer
60g of cyanated ethylene propylene diene monomer and 10g of activated Raney Ni catalyst are sequentially added into a flask filled with dimethylbenzene at 70 ℃, the reaction pressure is controlled to be 6MPa, and stirring reaction is carried out for 120min, so that the aminated ethylene propylene diene monomer is obtained.
(4) Synthesis of carboxylated carbon nanotubes
Adding the carbon nano tube into concentrated sulfuric acid and concentrated nitric acid solution with the volume ratio of 3:1, heating and refluxing for acidification, then adding 0.6g of acidified carbon nano tube, 1.8g of glutaric anhydride and toluene solvent into a flask in sequence at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature to obtain the carboxylated carbon nano tube.
(5) Synthesis of acyl chloride carbon nanotubes
And sequentially adding 12g of carboxylated carbon nanotubes, 24g of thionyl chloride and N, N-dimethylformamide solvent into a flask at 90 ℃, stirring uniformly, carrying out reflux reaction for 26 hours, washing with anhydrous tetrahydrofuran, and carrying out vacuum drying to obtain the carbon acyl chloride nanotubes.
(6) Synthesis of carbon nanotube grafted ethylene propylene diene monomer
Under the nitrogen atmosphere, 12g of acyl chloride carbon nano tube, 1.2g of amination ethylene propylene diene monomer, 1.2g of triethylamine and N, N-dimethylformamide solvent are sequentially added into a flask, reflux reaction is carried out for 20h at 70 ℃, and the carbon nano tube is cooled to room temperature, so that the carbon nano tube-connected ethylene propylene diene monomer is obtained.
(7) Synthesis of ethylene propylene diene monomer modified EVA material
200g of carbon nanotube grafted ethylene propylene diene monomer, 80g of EVA elastomer, 1g of hydroxyl silicone oil and 0.4g of vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are put into an open mill to be mixed for 8min, the mixed sizing material is put into the vulcanizing machine to be pressed for film for 25min at 160 ℃ and 12MPa, the mixed sizing material is put into an oven to be vulcanized for 6h at 175 ℃ and cooled to room temperature, and the ethylene propylene diene monomer modified EVA material is obtained.
Example 2
(1) Synthesis of cyanated ethylene propylene diene monomer
150g of ethylene propylene diene monomer is added into a flask filled with dimethylbenzene at 50 ℃ and stirred until the ethylene propylene diene monomer is completely dissolved, 7.5g of acrylonitrile and 0.75g of azodiisobutyronitrile are sequentially added into the flask at 65 ℃ under nitrogen atmosphere and stirred for 3 hours, acetone precipitation, N-dimethylformamide extraction and vacuum drying are carried out, and the cyano ethylene propylene diene monomer is obtained.
(2) Synthesis of activated Raney Ni catalyst
Grinding the nickel-aluminum alloy with the mass fraction of 40% in a ball mill, adding the ground nickel-aluminum alloy into a sodium hydroxide aqueous solution with the mass fraction of 20% at 60 ℃ for stirring reaction for 40min, and washing with distilled water to obtain the Raney Ni catalyst after the activation treatment.
(3) Synthesis of aminated ethylene propylene diene monomer
60g of cyanated ethylene propylene diene monomer and 6g of activated Raney Ni catalyst are sequentially added into a flask filled with dimethylbenzene at the temperature of 60 ℃, the reaction pressure is controlled to be 5MPa, and the mixture is stirred and reacted for 60 minutes to obtain the aminated ethylene propylene diene monomer.
(4) Synthesis of carboxylated carbon nanotubes
Adding the carbon nano tube into concentrated sulfuric acid and concentrated nitric acid solution with volume ratio of 3:1, heating and refluxing for acidification, then adding 0.6g of acidified carbon nano tube, 4g of glutaric anhydride and toluene solvent into a flask in sequence at 80 ℃, stirring for reaction for 5 hours, and cooling to room temperature to obtain the carboxylated carbon nano tube.
(5) Synthesis of acyl chloride carbon nanotubes
And sequentially adding 12g of carboxylated carbon nanotubes, 18g of thionyl chloride and N, N-dimethylformamide solvent into a flask at 70 ℃, stirring uniformly, carrying out reflux reaction for 20h, washing with anhydrous tetrahydrofuran, and carrying out vacuum drying to obtain the carbon acyl chloride nanotubes.
(6) Synthesis of carbon nanotube grafted ethylene propylene diene monomer
Under the nitrogen atmosphere, 12g of acyl chloride carbon nano tube, 1.2g of amination ethylene propylene diene monomer, 2.4g of triethylamine and N, N-dimethylformamide solvent are sequentially added into a flask, reflux reaction is carried out for 23h at 80 ℃, and the carbon nano tube is cooled to room temperature, so that the carbon nano tube-connected ethylene propylene diene monomer is obtained.
(7) Synthesis of ethylene propylene diene monomer modified EVA material
200g of carbon nanotube-connected ethylene propylene diene monomer, 20g of EVA elastomer, 0.2g of hydroxyl silicone oil and 0.2g of vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are put into an open mill to be mixed for 5min, the mixed sizing material is put into the vulcanizing machine to be pressed for 20min at 150 ℃ and 8MPa, and the mixed sizing material is put into an oven to be vulcanized for 4h at 170 ℃ and cooled to room temperature, so as to obtain the ethylene propylene diene monomer modified EVA material.
Example 3
(1) Synthesis of cyanated ethylene propylene diene monomer
150g of ethylene propylene diene monomer is added into a flask filled with dimethylbenzene at 50 ℃ and stirred until the ethylene propylene diene monomer is completely dissolved, 7.5g of acrylonitrile and 0.75g of azodiisobutyronitrile are sequentially added into the flask at 75 ℃ under nitrogen atmosphere and stirred for 4 hours, acetone precipitation, N-dimethylformamide extraction and vacuum drying are carried out, and the cyano ethylene propylene diene monomer is obtained.
(2) Synthesis of activated Raney Ni catalyst
Grinding the nickel-aluminum alloy with the mass fraction of 40% in a ball mill, adding the ground nickel-aluminum alloy into a sodium hydroxide aqueous solution with the mass fraction of 20% at 60 ℃ for stirring reaction for 50min, and washing with distilled water to obtain the Raney Ni catalyst after the activation treatment.
(3) Synthesis of aminated ethylene propylene diene monomer
60g of cyanated ethylene propylene diene monomer and 10g of activated Raney Ni catalyst are sequentially added into a flask filled with dimethylbenzene at 70 ℃, the reaction pressure is controlled to be 6MPa, and stirring reaction is carried out for 120min, so that the aminated ethylene propylene diene monomer is obtained.
(4) Synthesis of carboxylated carbon nanotubes
Adding the carbon nano tube into concentrated sulfuric acid and concentrated nitric acid solution with volume ratio of 3:1, heating and refluxing for acidification, then adding 0.6g of acidified carbon nano tube, 6g of glutaric anhydride and toluene solvent into a flask in sequence at 50 ℃, stirring for reaction for 2 hours, and cooling to room temperature to obtain the carboxylated carbon nano tube.
(5) Synthesis of acyl chloride carbon nanotubes
And sequentially adding 12g of carboxylated carbon nanotubes, 24g of thionyl chloride and N, N-dimethylformamide solvent into a flask at 70 ℃, stirring uniformly, carrying out reflux reaction for 20h, washing with anhydrous tetrahydrofuran, and carrying out vacuum drying to obtain the carbon acyl chloride nanotubes.
(6) Synthesis of carbon nanotube grafted ethylene propylene diene monomer
Under the nitrogen atmosphere, 12g of acyl chloride carbon nano tube, 3g of amination ethylene propylene diene monomer, 1.2g of triethylamine and N, N-dimethylformamide solvent are sequentially added into a flask, reflux reaction is carried out for 23h at 80 ℃, and cooling is carried out to room temperature, thus obtaining the carbon nano tube grafted ethylene propylene diene monomer.
(7) Synthesis of ethylene propylene diene monomer modified EVA material
200g of carbon nanotube grafted ethylene propylene diene monomer, 80g of EVA elastomer, 1g of hydroxyl silicone oil and 0.6g of vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are put into an open mill to be mixed for 10min, the mixed sizing material is put into the vulcanizing machine to be pressed for 30min at 170 ℃ and 12MPa, the mixed sizing material is put into an oven to be vulcanized for 6h at 180 ℃ and cooled to room temperature, and the ethylene propylene diene monomer modified EVA material is obtained.
Example 4
(1) Synthesis of cyanated ethylene propylene diene monomer
150g of ethylene propylene diene monomer is added into a flask filled with dimethylbenzene at 60 ℃ and stirred until the ethylene propylene diene monomer is completely dissolved, 10.5g of acrylonitrile and 0.9g of azodiisobutyronitrile are sequentially added into the flask at 75 ℃ under nitrogen atmosphere and stirred for reaction for 5 hours, acetone precipitation, N-dimethylformamide extraction and vacuum drying are carried out, and the cyano ethylene propylene diene monomer is obtained.
(2) Synthesis of activated Raney Ni catalyst
Grinding the nickel-aluminum alloy with the mass fraction of 40% in a ball mill, adding the ground nickel-aluminum alloy into a sodium hydroxide aqueous solution with the mass fraction of 20% at 60 ℃ for stirring reaction for 40min, and washing with distilled water to obtain the Raney Ni catalyst after the activation treatment.
(3) Synthesis of aminated ethylene propylene diene monomer
60g of cyanated ethylene propylene diene monomer and 12g of activated Raney Ni catalyst are sequentially added into a flask filled with dimethylbenzene at 80 ℃, the reaction pressure is controlled to be 7MPa, and stirring reaction is carried out for 140min, so that the aminated ethylene propylene diene monomer is obtained.
(4) Synthesis of carboxylated carbon nanotubes
Adding the carbon nano tube into concentrated sulfuric acid and concentrated nitric acid solution with the volume ratio of 3:1, heating and refluxing for acidification, then adding 0.6g of acidified carbon nano tube, 4g of glutaric anhydride and toluene solvent into a flask in sequence at 90 ℃, stirring for reaction for 3 hours, and cooling to room temperature to obtain the carboxylated carbon nano tube.
(5) Synthesis of acyl chloride carbon nanotubes
And sequentially adding 12g of carboxylated carbon nanotubes, 18g of thionyl chloride and N, N-dimethylformamide solvent into a flask at 80 ℃, stirring uniformly, carrying out reflux reaction for 20h, washing with anhydrous tetrahydrofuran, and carrying out vacuum drying to obtain the carbon acyl chloride nanotubes.
(6) Synthesis of carbon nanotube grafted ethylene propylene diene monomer
Under the nitrogen atmosphere, 12g of acyl chloride carbon nano tube, 3g of amination ethylene propylene diene monomer, 1.9g of triethylamine and N, N-dimethylformamide solvent are sequentially added into a flask, reflux reaction is carried out for 23h at 80 ℃, and cooling is carried out to room temperature, thus obtaining the carbon nano tube grafted ethylene propylene diene monomer.
(7) Synthesis of ethylene propylene diene monomer modified EVA material
200g of carbon nanotube-connected ethylene propylene diene monomer, 80g of EVA elastomer, 0.5g of hydroxyl silicone oil and 0.4g of vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are put into an open mill to be mixed for 8min, the mixed sizing material is put into the vulcanizing machine to be pressed for 30min at 150 ℃ and 12MPa, the mixed sizing material is put into an oven to be vulcanized for 5h at 170 ℃ and cooled to room temperature, and the ethylene propylene diene monomer modified EVA material is obtained.
Example 5
(1) Synthesis of cyanated ethylene propylene diene monomer
150g of ethylene propylene diene monomer is added into a flask filled with dimethylbenzene at 55 ℃ and stirred until the ethylene propylene diene monomer is completely dissolved, 8g of acrylonitrile and 0.8g of azodiisobutyronitrile are sequentially added into the flask and stirred for reaction for 4 hours under the nitrogen atmosphere at 70 ℃, acetone precipitation, N-dimethylformamide extraction and vacuum drying are carried out, and the cyano ethylene propylene diene monomer is obtained.
(2) Synthesis of activated Raney Ni catalyst
Grinding the nickel-aluminum alloy with the mass fraction of 40% in a ball mill, adding the ground nickel-aluminum alloy into a 30% sodium hydroxide aqueous solution at 70 ℃ for stirring reaction for 60min, and washing with distilled water to obtain the Raney Ni catalyst after the activation treatment.
(3) Synthesis of aminated ethylene propylene diene monomer
60g of cyanated ethylene propylene diene monomer and 10g of activated Raney Ni catalyst are sequentially added into a flask filled with dimethylbenzene at 70 ℃, the reaction pressure is controlled to be 6MPa, and stirring reaction is carried out for 120min, so that the aminated ethylene propylene diene monomer is obtained.
(4) Synthesis of carboxylated carbon nanotubes
Adding the carbon nano tube into concentrated sulfuric acid and concentrated nitric acid solution with volume ratio of 3:1, heating and refluxing for acidification, then adding 0.6g of acidified carbon nano tube, 6g of glutaric anhydride and toluene solvent into a flask in sequence at 100 ℃, stirring for reaction for 5 hours, and cooling to room temperature to obtain the carboxylated carbon nano tube.
(5) Synthesis of acyl chloride carbon nanotubes
And sequentially adding 12g of carboxylated carbon nanotubes, 20g of thionyl chloride and N, N-dimethylformamide solvent into a flask at 80 ℃, stirring uniformly, carrying out reflux reaction for 24 hours, washing with anhydrous tetrahydrofuran, and carrying out vacuum drying to obtain the carbon acyl chloride nanotubes.
(6) Synthesis of carbon nanotube grafted ethylene propylene diene monomer
Under the nitrogen atmosphere, 12g of acyl chloride carbon nano tube, 3.6g of amination ethylene propylene diene monomer, 2.4g of triethylamine and N, N-dimethylformamide solvent are sequentially added into a flask, reflux reaction is carried out for 26 hours at 90 ℃, and the carbon nano tube is cooled to room temperature, so that the carbon nano tube-connected ethylene propylene diene monomer is obtained.
(7) Synthesis of ethylene propylene diene monomer modified EVA material
200g of carbon nanotube-connected ethylene propylene diene monomer, 50g of EVA elastomer, 0.8g of hydroxyl silicone oil and 0.5g of vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are put into an open mill to be mixed for 8min, the mixed sizing material is put into the vulcanizing machine to be pressed for 25min at 160 ℃ and 10MPa, and the mixed sizing material is put into an oven to be vulcanized for 5h at 175 ℃ and cooled to room temperature, so as to obtain the ethylene propylene diene monomer modified EVA material.
The tensile properties were tested according to GB/T1040.2-2022, with a tensile rate of 500mm/min.
The tear strength was measured according to GB/T529-2008 with a tensile rate of 500mm/min.
Compression set performance was tested according to GB/T7759-2015.
Shore hardness was tested according to GB/T531.1-2008.
The tensile strength and Shore hardness of example 3 were the greatest, reaching 25.6MPa and 85 degrees. The tear strength of example 2 was maximum, reaching 18.4 kN.times.m -1 . The compression set of example 4 was maximum, reaching 32%.
Claims (7)
1. A synthesis process of ethylene propylene diene monomer modified EVA material is characterized in that: the synthesis process comprises the following steps:
(1) Synthesis of aminated ethylene propylene diene monomer
Sequentially adding cyano ethylene propylene diene monomer and an activated Raney Ni catalyst into a flask filled with dimethylbenzene at 60-80 ℃, controlling the reaction pressure to be 5-7MPa, and stirring for reacting for 60-140min to obtain amino ethylene propylene diene monomer;
(2) Synthesis of carbon nanotube grafted ethylene propylene diene monomer
Sequentially adding an acyl chloride carbon nano tube, an aminated ethylene propylene diene monomer, triethylamine and N, N-dimethylformamide into a flask under the nitrogen atmosphere, carrying out reflux reaction for 20-26h at 70-90 ℃, and cooling to room temperature to obtain the carbon nano tube grafted ethylene propylene diene monomer;
(3) Synthesis of ethylene propylene diene monomer modified EVA material
Adding carbon nanotube grafted ethylene propylene diene monomer, EVA elastomer, hydroxyl silicone oil and vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide into an open mill, mixing for 5-10min, placing the mixed sizing material into the vulcanizing machine at 150-170 ℃ and 8-12MPa for film pressing for 20-30min, placing into an oven at 170-180 ℃ for secondary vulcanization for 4-6h, and cooling to room temperature to obtain the ethylene propylene diene monomer modified EVA material.
2. The process for synthesizing the ethylene propylene diene monomer modified EVA material according to claim 1, which is characterized in that: the mass ratio of the cyanated ethylene propylene diene monomer to the Raney Ni catalyst in the step (1) is 1:0.1-0.2.
3. The process for synthesizing the ethylene propylene diene monomer modified EVA material according to claim 1, which is characterized in that: in the step (2), the mass ratio of the acyl chloride carbon nano tube to the amination ethylene propylene diene monomer to the triethylamine is 1:0.1-0.3:0.1-0.2.
4. The process for synthesizing the ethylene propylene diene monomer modified EVA material according to claim 1, which is characterized in that: in the step (3), the mass ratio of the carbon nano tube grafted ethylene propylene diene monomer rubber to the EVA elastomer to the hydroxyl silicone oil to the vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide is 1:0.1-0.4:0.01-0.05:0.01-0.03.
5. The process for synthesizing the ethylene propylene diene monomer modified EVA material according to claim 1, which is characterized in that: the synthesis process of the cyanated ethylene propylene diene monomer in the step (1) comprises the following steps:
adding ethylene propylene diene monomer into a flask filled with dimethylbenzene at 50-60 ℃ and stirring until the ethylene propylene diene monomer is completely dissolved, and sequentially adding acrylonitrile and azobisisobutyronitrile into the flask at 65-75 ℃ and stirring for reaction for 3-5h, wherein the mass ratio of the ethylene propylene diene monomer to the acrylonitrile to the azobisisobutyronitrile is 1:0.05-0.07:0.005-0.006, acetone precipitation, N-dimethylformamide extraction, vacuum drying to obtain cyano ethylene propylene diene monomer.
6. The process for synthesizing the ethylene propylene diene monomer modified EVA material according to claim 1, which is characterized in that: the synthesis process of the Raney Ni catalyst subjected to the activation treatment in the step (1) comprises the following steps:
grinding nickel-aluminum alloy with the mass fraction of 40% in a ball mill, adding the ground nickel-aluminum alloy into an aqueous solution containing 17-30% of sodium hydroxide with the mass fraction of 30% at 50-70 ℃ for stirring reaction for 30-60min, and washing with distilled water to obtain the Raney Ni catalyst after activation treatment.
7. The process for synthesizing the ethylene propylene diene monomer modified EVA material according to claim 1, which is characterized in that: the synthesis process of the acyl chloride carbon nano tube in the step (2) comprises the following steps:
s1, adding a carbon nano tube into concentrated sulfuric acid and concentrated nitric acid solution with volume ratio of 3:1, heating and refluxing for acidification, then sequentially adding the acidified carbon nano tube, glutaric anhydride and toluene into a flask at 50-100 ℃, wherein the mass ratio of the acidified carbon nano tube to the glutaric anhydride is 1:3-10, stirring and reacting for 2-5h, and cooling to room temperature to obtain carboxylated carbon nano tubes;
s2, sequentially adding carboxylated carbon nanotubes, thionyl chloride and N, N-dimethylformamide into a flask at the temperature of 70-90 ℃, wherein the mass ratio of the carboxylated carbon nanotubes to the thionyl chloride is 1:1.5-2, stirring uniformly, carrying out reflux reaction for 20-26h, washing with anhydrous tetrahydrofuran, and carrying out vacuum drying to obtain the carbon acyl chloride nanotubes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016090425A1 (en) * | 2014-12-08 | 2016-06-16 | The University Of Queensland | Nanocomposite elastomers |
| CN113698708A (en) * | 2021-09-07 | 2021-11-26 | 宁波工程学院 | Ethylene propylene diene monomer composition and preparation method thereof |
| CN114058039A (en) * | 2021-12-21 | 2022-02-18 | 易宝（福建）高分子材料股份公司 | Reversible crosslinked ethylene propylene diene monomer rubber and preparation method thereof |
| CN114933730A (en) * | 2022-06-13 | 2022-08-23 | 陈光岩 | Ethylene propylene diene monomer elastomer foam sponge material and preparation method thereof |
| CN115403846A (en) * | 2022-09-01 | 2022-11-29 | 杭州金泰塑业有限公司 | Nano-material HDPE (high-density polyethylene) pipe and production method thereof |
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| FR2957926A1 (en) * | 2010-03-25 | 2011-09-30 | Arkema France | PROCESS FOR THE PREPARATION OF ELASTOMERIC COMPOSITE MATERIAL |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016090425A1 (en) * | 2014-12-08 | 2016-06-16 | The University Of Queensland | Nanocomposite elastomers |
| CN113698708A (en) * | 2021-09-07 | 2021-11-26 | 宁波工程学院 | Ethylene propylene diene monomer composition and preparation method thereof |
| CN114058039A (en) * | 2021-12-21 | 2022-02-18 | 易宝（福建）高分子材料股份公司 | Reversible crosslinked ethylene propylene diene monomer rubber and preparation method thereof |
| CN114933730A (en) * | 2022-06-13 | 2022-08-23 | 陈光岩 | Ethylene propylene diene monomer elastomer foam sponge material and preparation method thereof |
| CN115403846A (en) * | 2022-09-01 | 2022-11-29 | 杭州金泰塑业有限公司 | Nano-material HDPE (high-density polyethylene) pipe and production method thereof |
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