CN118878906B - EVA foaming material and preparation process thereof - Google Patents
EVA foaming material and preparation process thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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Abstract
本发明涉及EVA发泡材料技术领域，具体为一种EVA发泡材料及其制备工艺。方案以EVA树脂为主要材料，加入聚酰胺弹性体、发泡剂、抗氧剂、相容剂、碳酸钙、包覆核壳氢氧化铝和硬脂酸钙，混炼后模压形成片材，再进行辐照交联，化学发泡形成EVA发泡材料；在该配方原料下，方案制备的EVA发泡材料的力学性能得到提升。同时，方案中以包覆核壳氢氧化铝作为阻燃剂，无需添加大量的阻燃剂分量即可实现较优异的阻燃性能，实用性较高。The present invention relates to the technical field of EVA foam materials, specifically to an EVA foam material and a preparation process thereof. The scheme uses EVA resin as the main material, adds polyamide elastomer, foaming agent, antioxidant, compatibilizer, calcium carbonate, coated core-shell aluminum hydroxide and calcium stearate, mixes and molds to form a sheet, and then irradiates and cross-links, and chemically foams to form an EVA foam material; under this formula of raw materials, the mechanical properties of the EVA foam material prepared by the scheme are improved. At the same time, the scheme uses coated core-shell aluminum hydroxide as a flame retardant, and can achieve relatively excellent flame retardant properties without adding a large amount of flame retardant components, and has high practicality.
Description
Technical Field
The invention relates to the technical field of EVA foaming materials, in particular to an EVA foaming material and a preparation process thereof.
Background
The EVA foaming material is one of the existing common foaming materials, has the advantages of good sound insulation, noise reduction, heat preservation, heat insulation, buffering, vibration reduction, easiness in processing and the like, can be widely applied to the fields of packaging, electronics, sports goods and the like, but the existing EVA foaming material on the market is poor in mechanical property, low in strength, poor in high-temperature resistance and low-temperature resistance and poor in rebound resilience, and the defects of the EVA foaming material greatly limit the practical application of the EVA foaming material.
Meanwhile, the EVA foaming agent purchased in the market is poor in flame retardant property, and cannot meet the requirements of consumers in application.
Disclosure of Invention
The invention aims to provide an EVA foaming material and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation process of EVA foaming material comprises the following steps:
Mixing aluminum hydroxide and absolute ethyl alcohol, performing ultrasonic dispersion for 20-30 min, adding phosphoric acid, reacting for 4-5 h at 70-75 ℃, filtering, washing, and vacuum drying to obtain coated powder, wherein the molar ratio of the aluminum hydroxide to the phosphoric acid is 1 (0.3-0.4);
Transferring the coated powder into a mixed solution of absolute ethyl alcohol and deionized water, adding tetraethoxysilane, stirring and reacting for 40-50 min, adding ammonia water, continuously reacting for 30-40 min, filtering and washing, and vacuum drying to obtain core-shell aluminum hydroxide;
Mixing core-shell aluminum hydroxide with deionized water, performing ultrasonic dispersion for 20-30 min, adding natural latex, stirring uniformly, adding 2% oxalic acid aqueous solution, demulsification and precipitation, washing with deionized water to be neutral, and performing vacuum drying to obtain coated core-shell aluminum hydroxide;
the dosage of the core-shell aluminum hydroxide accounts for 0.5-1wt% of the mass of the natural latex;
And (3) drying the polyamide elastomer at 90-100 ℃, mixing the dried polyamide elastomer with EVA resin, adding a foaming agent, an antioxidant, a compatilizer, calcium carbonate, coated core-shell aluminum hydroxide and calcium stearate, mixing for 10-20min, mixing for 10-15 min at 140-145 ℃, transferring to a press vulcanizer for mould pressing for 2-3 min to form a sheet, crosslinking the sheet under the irradiation dose of 70KGy, and foaming for 2-3 min in a 240 ℃ foaming furnace to form the EVA foaming material.
In the optimized scheme, in the step (3), the mass fraction of each component is 10-12 wt% of polyamide elastomer, 10-15 wt% of foaming agent, 1-2 wt% of antioxidant, 3-4 wt% of compatilizer, 2-3 wt% of calcium carbonate, 25-40 wt% of coated core-shell aluminum hydroxide, 0.5-1 wt% of calcium stearate and the balance of EVA resin.
In the more optimized scheme, in the step (3), the molding temperature is 110-120 ℃, the molding pressure is 8-10 MPa, the foaming agent is azodicarbonamide, and the antioxidant is antioxidant 1010.
In a more optimized scheme, in the step (3), the preparation method of the polyamide elastomer comprises the following steps:
S1, mixing dodecadiamine and dodecadiacid, then putting the mixture into a reaction kettle, adding deionized water and an antioxidant, wherein the replacement atmosphere is nitrogen, heating to 150-155 ℃, carrying out heat preservation reaction for 30-40 min, heating to 200-205 ℃, discharging to normal pressure, discharging, and crushing to obtain a prepolymer;
S2, mixing the prepolymer and the polytetrahydrofuran, then putting the mixture into a reaction kettle, adding an antioxidant and modified aluminum hydroxide, replacing the atmosphere with nitrogen, heating to 215-220 ℃, carrying out heat preservation reaction for 2-2.5 h, discharging to normal pressure, adding tetrabutyl titanate, vacuumizing and heating to 250-255 ℃, carrying out pressure of 200-300 MPa, filling nitrogen, recovering to normal pressure, and discharging to obtain the polyamide elastomer.
In the optimized scheme, in S1, the molar ratio of the dodecadiamine to the dodecadiacid is 1 (1.5-2), the dosage of deionized water is 30wt% of the total mass of the dodecadiamine and the dodecadiacid, and the dosage of the antioxidant is 2-3 wt% of the total mass of the dodecadiamine and the dodecadiacid.
In the optimized scheme, in S2, the molar ratio of the prepolymer to the polytetrahydrofuran is 1:1, the amount of the antioxidant is 2-3wt% of the total mass of the system, the amount of the tetrabutyl titanate is 2-3wt% of the total mass of the system, and the amount of the modified aluminum hydroxide is 2-3wt% of the total mass of the system.
The preparation method of the modified aluminum hydroxide comprises the steps of mixing core-shell aluminum hydroxide and a silane coupling agent, heating to 120-130 ℃, stirring for reacting for 2-3 hours, wherein the stirring speed is 1000-1200 r/min, and the modified core-shell aluminum hydroxide is obtained, and the silane coupling agent is KH-550, and the dosage is 2-3 wt% of the core-shell aluminum hydroxide.
And (3) according to an optimized scheme, the EVA foaming material prepared by the preparation process is prepared.
Compared with the prior art, the invention has the following beneficial effects:
The invention discloses a preparation process of EVA foaming material, which adopts EVA resin as main material, and adds polyamide elastomer, foaming agent, antioxidant, compatilizer, calcium carbonate, coated core-shell aluminum hydroxide and calcium stearate, after mixing, molding to form sheet, then carrying out irradiation crosslinking, and chemical foaming to form EVA foaming material, wherein under the condition of the formula raw materials, the mechanical property of EVA foaming material prepared by the scheme is improved. Meanwhile, in the scheme, the coated core-shell aluminum hydroxide is used as the flame retardant, so that excellent flame retardant performance can be realized without adding a large amount of flame retardant components, and the practicability is high.
According to the scheme, firstly, aluminum hydroxide is taken as a core, phosphoric acid is added for reaction, aluminum phosphate is generated on the surface of the core, so that coated powder is obtained, then, the coated powder is taken as the core, silicon dioxide is taken as a shell layer, the core-shell aluminum hydroxide is added into an EVA foaming system as a flame retardant, so that the flame retardant performance of a product can be effectively improved, meanwhile, in order to avoid the problem of poor compatibility of the flame retardant and the system, natural latex is used for coating the core-shell aluminum hydroxide to form coated core-shell aluminum hydroxide, so that the dispersibility of a flame retardant component in the system is improved, and the comprehensive performance of the product is ensured.
On the other hand, the scheme utilizes the reaction of the dodecyl diamine and the dodecyl dibasic acid to generate a prepolymer, then the prepolymer is mixed with the polytetrahydrofuran to react to generate the polyamide elastomer, the introduction of the polyamide elastomer can improve the mechanical property and the tensile strength of the product, and the scheme also adds the core-shell aluminum hydroxide modified by the aminosilane coupling agent during the preparation of the polyamide elastomer, and further cooperates with the coated core-shell aluminum hydroxide to realize flame retardance.
The invention discloses a preparation process of an EVA foaming material, which has reasonable process design after the formula raw materials are subjected to multiple adjustment and compounding, and the prepared EVA foaming material has the advantages of improved mechanical properties, excellent flame retardant property, wide application in multiple fields and excellent practicability.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious 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.
In this example, natural latex, industrial grade, was purchased from new materials technology limited in Shandong, EVA resin model Y2022, VA=14%, compatibilizer model C250, was purchased from DuPont, USA, foaming agent azodicarbonamide, antioxidant 1010. The molecular weight of polytetrahydrofuran is 2000.
Example 1A preparation process of EVA foaming material, comprising the following steps:
Mixing 1mol of aluminum hydroxide with 500mL of absolute ethyl alcohol, performing ultrasonic dispersion for 20min, adding 0.4mol of phosphoric acid, reacting for 5h at 70 ℃, filtering, washing, and vacuum drying to obtain coated powder, transferring 1g of coated powder into a mixed solution of 55mL of absolute ethyl alcohol and 15mL of deionized water, adding 45mL of tetraethoxysilane, stirring and reacting for 40min, adding ammonia water, continuing to react for 40min, filtering, washing, and vacuum drying to obtain the core-shell aluminum hydroxide.
And (2) mixing core-shell aluminum hydroxide with deionized water, performing ultrasonic dispersion for 20min, adding natural latex, stirring uniformly, adding 2% oxalic acid aqueous solution, performing demulsification precipitation, washing with deionized water to be neutral, and performing vacuum drying to obtain the coated core-shell aluminum hydroxide, wherein the dosage of the core-shell aluminum hydroxide accounts for 1wt% of the mass of the natural latex.
And (3) drying the polyamide elastomer at 90 ℃, mixing the dried polyamide elastomer with EVA resin, adding a foaming agent, an antioxidant, a compatilizer, calcium carbonate, coated core-shell aluminum hydroxide and calcium stearate, mixing for 10min, mixing for 15min at 140 ℃, transferring to a press vulcanizer for molding for 3min at 120 ℃ under the molding pressure of 10MPa to form a sheet, and crosslinking the sheet under the irradiation dose of 70KGy for 3min in a 240 ℃ foaming furnace to form the EVA foaming material.
In the step (3), the weight percentages of the components are, by mass, 10% of polyamide elastomer, 15% of foaming agent, 1.5% of antioxidant, 3% of compatilizer, 2% of calcium carbonate, 25% of coated core-shell aluminum hydroxide, 0.5% of calcium stearate and the balance EVA resin. The foaming agent is azodicarbonamide and the antioxidant is antioxidant 1010.
The preparation method of the polyamide elastomer comprises the following steps:
S1, mixing the dodecadiamine and the dodecadiacid, then putting the mixture into a reaction kettle, adding deionized water and an antioxidant, wherein the replacement atmosphere is nitrogen, heating to 150 ℃, carrying out heat preservation reaction for 40min, heating to 200 ℃, discharging to normal pressure, discharging, and crushing to obtain a prepolymer, wherein the molar ratio of the dodecadiamine to the dodecadiacid is 1:2, the deionized water is 30wt% of the total mass of the dodecadiamine and the dodecadiacid, and the antioxidant is 2wt% of the total mass of the dodecadiamine and the dodecadiacid.
The preparation method of the modified aluminum hydroxide comprises the steps of mixing core-shell aluminum hydroxide and a silane coupling agent, heating to 120 ℃, stirring and reacting for 3 hours, wherein the stirring speed is 1000r/min, and the modified core-shell aluminum hydroxide is obtained, and the silane coupling agent is KH-550, and the dosage is 2wt% of the core-shell aluminum hydroxide.
S2, mixing the prepolymer and the polytetrahydrofuran, then putting the mixture into a reaction kettle, adding an antioxidant and modified aluminum hydroxide, heating to 215 ℃ in a replacement atmosphere of nitrogen, carrying out heat preservation reaction for 2.5 hours, discharging to normal pressure, adding tetrabutyl titanate, vacuumizing and heating to 250 ℃, keeping the pressure at 200MPa, filling nitrogen to normal pressure, and discharging to obtain the polyamide elastomer. The molar ratio of the prepolymer to the polytetrahydrofuran is 1:1, the dosage of the antioxidant is 2wt% of the total mass of the system, the dosage of the tetrabutyl titanate is 2wt% of the total mass of the system, and the dosage of the modified aluminum hydroxide is 2wt% of the total mass of the system.
Example 2A preparation process of EVA foaming material, comprising the following steps:
mixing 1mol of aluminum hydroxide with 500mL of absolute ethyl alcohol, performing ultrasonic dispersion for 25min, adding 0.4mol of phosphoric acid, reacting for 4.5h at 75 ℃, filtering, washing, and vacuum drying to obtain coated powder, transferring 1g of coated powder into a mixed solution of 55mL of absolute ethyl alcohol and 15mL of deionized water, adding 45mL of ethyl orthosilicate, stirring and reacting for 45min, adding ammonia water, continuing to react for 35min, filtering, washing, and vacuum drying to obtain core-shell aluminum hydroxide.
And (2) mixing core-shell aluminum hydroxide and deionized water, performing ultrasonic dispersion for 25min, adding natural latex, stirring uniformly, adding 2% oxalic acid aqueous solution, performing demulsification precipitation, washing with deionized water to be neutral, and performing vacuum drying to obtain the coated core-shell aluminum hydroxide, wherein the dosage of the core-shell aluminum hydroxide accounts for 1wt% of the mass of the natural latex.
And (3) drying the polyamide elastomer at 95 ℃, mixing the dried polyamide elastomer with EVA resin, adding a foaming agent, an antioxidant, a compatilizer, calcium carbonate, coated core-shell aluminum hydroxide and calcium stearate, mixing for 15min and 145 ℃ and mixing for 15min, transferring to a press vulcanizer for molding for 3min, wherein the molding temperature is 120 ℃ and the molding pressure is 10MPa, forming a sheet, and crosslinking the sheet under the condition that the irradiation dose is 70KGy, foaming for 3min in a 240 ℃ foaming furnace, thus forming the EVA foaming material.
In the step (3), the weight percentages of the components are 11 percent of polyamide elastomer, 15 percent of foaming agent, 1.5 percent of antioxidant, 3 percent of compatilizer, 2 percent of calcium carbonate, 25 percent of coated core-shell aluminum hydroxide, 0.5 percent of calcium stearate and the balance of EVA resin. The foaming agent is azodicarbonamide and the antioxidant is antioxidant 1010.
The preparation method of the polyamide elastomer comprises the following steps:
s1, mixing the dodecadiamine and the dodecadiacid, then putting the mixture into a reaction kettle, adding deionized water and an antioxidant, wherein the replacement atmosphere is nitrogen, heating to 155 ℃, carrying out heat preservation reaction for 35min, heating to 205 ℃, discharging to normal pressure, discharging, and crushing to obtain a prepolymer, wherein the molar ratio of the dodecadiamine to the dodecadiacid is 1:2, the deionized water is 30wt% of the total mass of the dodecadiamine and the dodecadiacid, and the antioxidant is 2wt% of the total mass of the dodecadiamine and the dodecadiacid.
The preparation method of the modified aluminum hydroxide comprises the steps of mixing core-shell aluminum hydroxide and a silane coupling agent, heating to 125 ℃, stirring and reacting for 2.5h, wherein the stirring speed is 1000r/min, and the modified core-shell aluminum hydroxide is obtained, and the silane coupling agent is KH-550, and the dosage is 2wt% of the core-shell aluminum hydroxide.
S2, mixing the prepolymer and the polytetrahydrofuran, then putting the mixture into a reaction kettle, adding an antioxidant and modified aluminum hydroxide, heating to 215 ℃ in a replacement atmosphere of nitrogen, carrying out heat preservation reaction for 2.5 hours, discharging to normal pressure, adding tetrabutyl titanate, vacuumizing and heating to 250 ℃, keeping the pressure at 200MPa, filling nitrogen to normal pressure, and discharging to obtain the polyamide elastomer. The molar ratio of the prepolymer to the polytetrahydrofuran is 1:1, the dosage of the antioxidant is 2wt% of the total mass of the system, the dosage of the tetrabutyl titanate is 2wt% of the total mass of the system, and the dosage of the modified aluminum hydroxide is 2wt% of the total mass of the system.
Example 3A preparation process of EVA foaming material, comprising the following steps:
Mixing 1mol of aluminum hydroxide with 500mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min, adding 0.4mol of phosphoric acid, reacting for 4h at 75 ℃, filtering, washing, and vacuum drying to obtain coated powder, transferring 1g of coated powder into a mixed solution of 55mL of absolute ethyl alcohol and 15mL of deionized water, adding 45mL of tetraethoxysilane, stirring and reacting for 50min, adding ammonia water, continuing to react for 40min, filtering, washing, and vacuum drying to obtain the core-shell aluminum hydroxide.
And (2) mixing core-shell aluminum hydroxide with deionized water, performing ultrasonic dispersion for 30min, adding natural latex, stirring uniformly, adding 2% oxalic acid aqueous solution, performing demulsification precipitation, washing with deionized water to be neutral, and performing vacuum drying to obtain the coated core-shell aluminum hydroxide, wherein the dosage of the core-shell aluminum hydroxide accounts for 1wt% of the mass of the natural latex.
And (3) drying the polyamide elastomer at 100 ℃, mixing the dried polyamide elastomer with EVA resin, adding a foaming agent, an antioxidant, a compatilizer, calcium carbonate, coated core-shell aluminum hydroxide and calcium stearate, mixing for 20min, mixing for 10min at 145 ℃, transferring to a press vulcanizer for molding for 3min at 120 ℃ under 10MPa to form a sheet, and crosslinking the sheet under the condition of 70KGy of irradiation dose and foaming for 3min in a 240 ℃ foaming furnace to form the EVA foaming material.
In the step (3), the weight percentages of the components are, by mass, 12% of polyamide elastomer, 15% of foaming agent, 1.5% of antioxidant, 3% of compatilizer, 2% of calcium carbonate, 25% of coated core-shell aluminum hydroxide, 0.5% of calcium stearate and the balance EVA resin. The foaming agent is azodicarbonamide and the antioxidant is antioxidant 1010.
The preparation method of the polyamide elastomer comprises the following steps:
S1, mixing the dodecadiamine and the dodecadiacid, then putting the mixture into a reaction kettle, adding deionized water and an antioxidant, wherein the replacement atmosphere is nitrogen, heating to 155 ℃, carrying out heat preservation reaction for 30min, heating to 205 ℃, discharging to normal pressure, discharging, and crushing to obtain a prepolymer, wherein the molar ratio of the dodecadiamine to the dodecadiacid is 1:2, the deionized water is 30wt% of the total mass of the dodecadiamine and the dodecadiacid, and the antioxidant is 2wt% of the total mass of the dodecadiamine and the dodecadiacid.
The preparation method of the modified aluminum hydroxide comprises the steps of mixing core-shell aluminum hydroxide and a silane coupling agent, heating to 130 ℃, stirring and reacting for 2 hours, wherein the stirring speed is 1000r/min, and the modified core-shell aluminum hydroxide is obtained, and the silane coupling agent is KH-550, and the dosage is 2wt% of the core-shell aluminum hydroxide.
S2, mixing the prepolymer and the polytetrahydrofuran, then putting the mixture into a reaction kettle, adding an antioxidant and modified aluminum hydroxide, heating to 220 ℃ in a replacement atmosphere of nitrogen, carrying out heat preservation reaction for 2 hours, discharging to normal pressure, adding tetrabutyl titanate, vacuumizing and heating to 250 ℃, keeping the pressure at 200MPa, filling nitrogen to normal pressure, and discharging to obtain the polyamide elastomer. The molar ratio of the prepolymer to the polytetrahydrofuran is 1:1, the dosage of the antioxidant is 2wt% of the total mass of the system, the dosage of the tetrabutyl titanate is 2wt% of the total mass of the system, and the dosage of the modified aluminum hydroxide is 2wt% of the total mass of the system.
Comparative example 1 Using example 3 as a control group, the natural latex coating was not used in comparative example 1, and the remaining process steps were unchanged.
A preparation process of EVA foaming material comprises the following steps:
Mixing 1mol of aluminum hydroxide with 500mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min, adding 0.4mol of phosphoric acid, reacting for 4h at 75 ℃, filtering, washing, and vacuum drying to obtain coated powder, transferring 1g of coated powder into a mixed solution of 55mL of absolute ethyl alcohol and 15mL of deionized water, adding 45mL of tetraethoxysilane, stirring and reacting for 50min, adding ammonia water, continuing to react for 40min, filtering, washing, and vacuum drying to obtain the core-shell aluminum hydroxide.
And (2) drying the polyamide elastomer at 100 ℃, mixing the dried polyamide elastomer with EVA resin, adding a foaming agent, an antioxidant, a compatilizer, calcium carbonate, core-shell aluminum hydroxide and calcium stearate, mixing for 20min, mixing for 10min at 145 ℃, transferring to a press vulcanizer for molding for 3min at 120 ℃ under 10MPa to form a sheet, and crosslinking the sheet under the condition of 70KGy of irradiation dose and foaming for 3min in a 240 ℃ foaming furnace to form the EVA foaming material.
In the step (3), the weight percentages of the components are, by mass, 12% of a polyamide elastomer, 15% of a foaming agent, 1.5% of an antioxidant, 3% of a compatilizer, 2% of calcium carbonate, 25% of core-shell aluminum hydroxide, 0.5% of calcium stearate and the balance of EVA resin. The foaming agent is azodicarbonamide and the antioxidant is antioxidant 1010.
The preparation method of the polyamide elastomer comprises the following steps:
S1, mixing the dodecadiamine and the dodecadiacid, then putting the mixture into a reaction kettle, adding deionized water and an antioxidant, wherein the replacement atmosphere is nitrogen, heating to 155 ℃, carrying out heat preservation reaction for 30min, heating to 205 ℃, discharging to normal pressure, discharging, and crushing to obtain a prepolymer, wherein the molar ratio of the dodecadiamine to the dodecadiacid is 1:2, the deionized water is 30wt% of the total mass of the dodecadiamine and the dodecadiacid, and the antioxidant is 2wt% of the total mass of the dodecadiamine and the dodecadiacid.
The preparation method of the modified aluminum hydroxide comprises the steps of mixing core-shell aluminum hydroxide and a silane coupling agent, heating to 130 ℃, stirring and reacting for 2 hours, wherein the stirring speed is 1000r/min, and the modified core-shell aluminum hydroxide is obtained, and the silane coupling agent is KH-550, and the dosage is 2wt% of the core-shell aluminum hydroxide.
S2, mixing the prepolymer and the polytetrahydrofuran, then putting the mixture into a reaction kettle, adding an antioxidant and modified aluminum hydroxide, heating to 220 ℃ in a replacement atmosphere of nitrogen, carrying out heat preservation reaction for 2 hours, discharging to normal pressure, adding tetrabutyl titanate, vacuumizing and heating to 250 ℃, keeping the pressure at 200MPa, filling nitrogen to normal pressure, and discharging to obtain the polyamide elastomer. The molar ratio of the prepolymer to the polytetrahydrofuran is 1:1, the dosage of the antioxidant is 2wt% of the total mass of the system, the dosage of the tetrabutyl titanate is 2wt% of the total mass of the system, and the dosage of the modified aluminum hydroxide is 2wt% of the total mass of the system.
Comparative example 2 with example 3 as the control, in comparative example 2, modified core-shell aluminum hydroxide was not added to the polyamide elastomer, and the remaining process steps were unchanged.
A preparation process of EVA foaming material comprises the following steps:
Mixing 1mol of aluminum hydroxide with 500mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min, adding 0.4mol of phosphoric acid, reacting for 4h at 75 ℃, filtering, washing, and vacuum drying to obtain coated powder, transferring 1g of coated powder into a mixed solution of 55mL of absolute ethyl alcohol and 15mL of deionized water, adding 45mL of tetraethoxysilane, stirring and reacting for 50min, adding ammonia water, continuing to react for 40min, filtering, washing, and vacuum drying to obtain the core-shell aluminum hydroxide.
And (2) mixing core-shell aluminum hydroxide with deionized water, performing ultrasonic dispersion for 30min, adding natural latex, stirring uniformly, adding 2% oxalic acid aqueous solution, performing demulsification precipitation, washing with deionized water to be neutral, and performing vacuum drying to obtain the coated core-shell aluminum hydroxide, wherein the dosage of the core-shell aluminum hydroxide accounts for 1wt% of the mass of the natural latex.
And (3) drying the polyamide elastomer at 100 ℃, mixing the dried polyamide elastomer with EVA resin, adding a foaming agent, an antioxidant, a compatilizer, calcium carbonate, coated core-shell aluminum hydroxide and calcium stearate, mixing for 20min, mixing for 10min at 145 ℃, transferring to a press vulcanizer for molding for 3min at 120 ℃ under 10MPa to form a sheet, and crosslinking the sheet under the condition of 70KGy of irradiation dose and foaming for 3min in a 240 ℃ foaming furnace to form the EVA foaming material.
In the step (3), the weight percentages of the components are, by mass, 12% of polyamide elastomer, 15% of foaming agent, 1.5% of antioxidant, 3% of compatilizer, 2% of calcium carbonate, 25% of coated core-shell aluminum hydroxide, 0.5% of calcium stearate and the balance EVA resin. The foaming agent is azodicarbonamide and the antioxidant is antioxidant 1010.
The preparation method of the polyamide elastomer comprises the following steps:
S1, mixing the dodecadiamine and the dodecadiacid, then putting the mixture into a reaction kettle, adding deionized water and an antioxidant, wherein the replacement atmosphere is nitrogen, heating to 155 ℃, carrying out heat preservation reaction for 30min, heating to 205 ℃, discharging to normal pressure, discharging, and crushing to obtain a prepolymer, wherein the molar ratio of the dodecadiamine to the dodecadiacid is 1:2, the deionized water is 30wt% of the total mass of the dodecadiamine and the dodecadiacid, and the antioxidant is 2wt% of the total mass of the dodecadiamine and the dodecadiacid.
S2, mixing the prepolymer and the polytetrahydrofuran, then putting the mixture into a reaction kettle, adding an antioxidant, heating to 220 ℃ in a replacement atmosphere of nitrogen, carrying out heat preservation reaction for 2 hours, discharging to normal pressure, adding tetrabutyl titanate, vacuumizing and heating to 250 ℃, keeping the pressure at 200MPa, charging nitrogen, recovering to normal pressure, and discharging to obtain the polyamide elastomer. The molar ratio of the prepolymer to the polytetrahydrofuran is 1:1, the dosage of the antioxidant is 2wt% of the total mass of the system, and the dosage of the tetrabutyl titanate is 2wt% of the total mass of the system.
Comparative example 3 with example 3 as the control, only aluminum hydroxide was added as a flame retardant in comparative example 3, with the remaining process steps unchanged.
A preparation process of EVA foaming material comprises the following steps:
Mixing aluminum hydroxide and deionized water, performing ultrasonic dispersion for 30min, adding natural latex, uniformly stirring, adding 2% oxalic acid aqueous solution, performing demulsification and precipitation, washing the deionized water to be neutral, and performing vacuum drying to obtain coated aluminum hydroxide, wherein the use amount of the aluminum hydroxide is 1wt% of the mass of the natural latex.
And (2) drying the polyamide elastomer at 100 ℃, mixing the dried polyamide elastomer with EVA resin, adding a foaming agent, an antioxidant, a compatilizer, calcium carbonate, coated aluminum hydroxide and calcium stearate, mixing for 20min, mixing for 10min at 145 ℃, transferring to a press vulcanizer for molding for 3min at 120 ℃ under 10MPa to form a sheet, crosslinking the sheet under the condition of 70KGy of irradiation dose, and foaming for 3min in a 240 ℃ foaming furnace to form the EVA foaming material.
In the step (3), the weight percentages of the components are, by mass, 12% of a polyamide elastomer, 15% of a foaming agent, 1.5% of an antioxidant, 3% of a compatilizer, 2% of calcium carbonate, 25% of coated aluminum hydroxide, 0.5% of calcium stearate and the balance of EVA resin. The foaming agent is azodicarbonamide and the antioxidant is antioxidant 1010.
The preparation method of the polyamide elastomer comprises the following steps:
S1, mixing the dodecadiamine and the dodecadiacid, then putting the mixture into a reaction kettle, adding deionized water and an antioxidant, wherein the replacement atmosphere is nitrogen, heating to 155 ℃, carrying out heat preservation reaction for 30min, heating to 205 ℃, discharging to normal pressure, discharging, and crushing to obtain a prepolymer, wherein the molar ratio of the dodecadiamine to the dodecadiacid is 1:2, the deionized water is 30wt% of the total mass of the dodecadiamine and the dodecadiacid, and the antioxidant is 2wt% of the total mass of the dodecadiamine and the dodecadiacid.
S2, mixing the prepolymer and the polytetrahydrofuran, then putting the mixture into a reaction kettle, adding an antioxidant and aluminum hydroxide, heating to 220 ℃ in a replacement atmosphere of nitrogen, carrying out heat preservation reaction for 2 hours, discharging to normal pressure, adding tetrabutyl titanate, vacuumizing and heating to 250 ℃, keeping the pressure at 200MPa, filling nitrogen to normal pressure, and discharging to obtain the polyamide elastomer. The molar ratio of the prepolymer to the polytetrahydrofuran is 1:1, the dosage of the antioxidant is 2wt% of the total mass of the system, the dosage of the tetrabutyl titanate is 2wt% of the total mass of the system, and the dosage of the aluminum hydroxide is 2wt% of the total mass of the system.
Detection experiment:
The foam sample bars prepared in examples 1 to 3 and comparative examples 1 to 3 were prepared into dumbbell shapes, the tensile properties were tested with reference to GB/T6344 at a tensile speed of 500mm/min, the rebound rate was tested with reference to GB/T6670, the sample specifications were 100 mm. Times.100 mm. Times.50 mm, the drop height of the steel balls was 460mm, and the limiting oxygen index of the samples was tested.
| Project | Tensile strength MPa | Rebound% | Limiting oxygen index |
| Example 1 | 0.44 | 58.6 | 37.9 |
| Example 2 | 0.46 | 58.9 | 38.4 |
| Example 3 | 0.49 | 59.3 | 38.8 |
| Comparative example 1 | 0.45 | 58.8 | 37.5 |
| Comparative example 2 | 0.47 | 59.1 | 34.2 |
| Comparative example 3 | 0.41 | 57.2 | 29.8 |
Conclusion is that the invention discloses a preparation process of EVA foaming material, the formula raw materials in the whole scheme are subjected to multiple adjustment and compounding, the process design is reasonable, the mechanical property of the prepared EVA foaming material is improved, the flame retardant property is excellent, the EVA foaming material can be widely applied to multiple fields, and the practicability is excellent.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and the present invention is not limited thereto, but may be modified or substituted for some of the technical features thereof by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A preparation process of EVA foaming material is characterized by comprising the following steps:
Mixing aluminum hydroxide and absolute ethyl alcohol, performing ultrasonic dispersion for 20-30 min, adding phosphoric acid, reacting for 4-5 h at 70-75 ℃, filtering, washing and vacuum drying to obtain coated powder;
Transferring the coated powder into a mixed solution of absolute ethyl alcohol and deionized water, adding tetraethoxysilane, stirring and reacting for 40-50 min, adding ammonia water, continuously reacting for 30-40 min, filtering and washing, and vacuum drying to obtain core-shell aluminum hydroxide;
Mixing core-shell aluminum hydroxide with deionized water, performing ultrasonic dispersion for 20-30 min, adding natural latex, stirring uniformly, adding oxalic acid aqueous solution, demulsification and precipitation, washing with deionized water to be neutral, and performing vacuum drying to obtain coated core-shell aluminum hydroxide;
drying the polyamide elastomer at 90-100 ℃, mixing the dried polyamide elastomer with EVA resin, adding a foaming agent, an antioxidant, a compatilizer, calcium carbonate, coated core-shell aluminum hydroxide and calcium stearate, mixing for 10-20 min, mixing for 10-15 min at 140-145 ℃, transferring to a press vulcanizer for mould pressing for 2-3 min to form a sheet, crosslinking the sheet under the irradiation dose of 70KGy, and foaming for 2-3 min in a 240 ℃ foaming furnace to form an EVA foaming material;
in the step (3), the dosages of the components are, by mass, 10-12% of polyamide elastomer, 10-15% of foaming agent, 1-2% of antioxidant, 3-4% of compatilizer, 2-3% of calcium carbonate, 25-40% of coated core-shell aluminum hydroxide, 0.5-1% of calcium stearate and the balance EVA resin;
in the step (3), the preparation method of the polyamide elastomer comprises the following steps:
S1, mixing dodecadiamine and dodecadiacid, then putting the mixture into a reaction kettle, adding deionized water and an antioxidant, wherein the replacement atmosphere is nitrogen, heating to 150-155 ℃, carrying out heat preservation reaction for 30-40 min, heating to 200-205 ℃, discharging to normal pressure, discharging, and crushing to obtain a prepolymer;
S2, mixing the prepolymer and polytetrahydrofuran, then putting the mixture into a reaction kettle, adding an antioxidant and modified core-shell aluminum hydroxide, replacing the atmosphere with nitrogen, heating to 215-220 ℃, carrying out heat preservation reaction for 2-2.5 h, discharging to normal pressure, adding tetrabutyl titanate, vacuumizing and heating to 250-255 ℃, wherein the pressure is 200-300 MPa, filling nitrogen to normal pressure, and discharging to obtain the polyamide elastomer;
the preparation method of the modified core-shell aluminum hydroxide comprises the steps of mixing the core-shell aluminum hydroxide with a silane coupling agent, heating to 120-130 ℃, stirring and reacting for 2-3 hours, wherein the stirring speed is 1000-1200 r/min, and the silane coupling agent is KH-550, and the dosage is 2-3 wt% of the core-shell aluminum hydroxide.
2. The preparation process of the EVA foaming material is characterized in that in the step (3), the molding temperature is 110-120 ℃, the molding pressure is 8-10 MPa, the foaming agent is azodicarbonamide, and the antioxidant is antioxidant 1010.
3. The preparation process of the EVA foaming material is characterized in that in S1, the molar ratio of the dodecadiamine to the dodecadiacid is 1 (1.5-2), the deionized water is 30wt% of the total mass of the dodecadiamine and the dodecadiacid, and the antioxidant is 2-3 wt% of the total mass of the dodecadiamine and the dodecadiacid.
4. The preparation process of the EVA foaming material is characterized in that in S2, the molar ratio of the prepolymer to the polytetrahydrofuran is 1:1, the amount of the antioxidant is 2-3wt% of the total mass of the system, the amount of the tetrabutyl titanate is 2-3wt% of the total mass of the system, and the amount of the modified core-shell aluminum hydroxide is 2-3wt% of the total mass of the system.
5. The EVA foam material prepared by the preparation process according to any one of claims 1 to 4.
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| CN110903513A (en) * | 2019-12-03 | 2020-03-24 | 苏州诺博恩新材料科技有限公司 | Silicon dioxide core-shell antibacterial flame retardant and preparation method thereof |
| CN118126438A (en) * | 2024-02-21 | 2024-06-04 | 浙江红蜻蜓鞋业股份有限公司 | Anti-skid wear-resistant EVA composite shoe material and preparation method thereof |
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| CN110903513A (en) * | 2019-12-03 | 2020-03-24 | 苏州诺博恩新材料科技有限公司 | Silicon dioxide core-shell antibacterial flame retardant and preparation method thereof |
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