Eva / poe composite high resilience foam material and preparation method thereof

Abstract

The application belongs to the technical field of foamed material manufacturing, and particularly relates to EVA / POE composite high-resilience foamed material and a preparation method thereof. The EVA / POE composite high-resilience foamed material is prepared by mixing EVA, POE, a foaming agent, a foaming aid, a foaming stabilizer and a crosslinking agent, and then extruding and vulcanizing, and twice foaming. The modified nucleation flame retardant prepared by loading a modified flame retardant on a porous metal frame and mixing with polydimethylsiloxane as the foaming stabilizer provides a large number of gas nucleation sites, so that the bubble size is refined and distributed more uniformly. The modified flame retardant is fixed in the micropores of the porous metal frame through hydrogen bonds, so that the modified nucleation flame retardant has both bubble nucleation stability and flame retardancy. The high-resilience foamed material prepared by the application has ideal foaming quality, excellent resilience, impact resilience and flame retardancy.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of foamed material manufacturing, and particularly relates to EVA / POE composite high-resilience foamed material and a preparation method thereof. BACKGROUND

[0002] Ethylene-vinyl acetate copolymer (EVA) is a kind of foamed material with no toxicity, good mechanical properties and elasticity. By introducing vinyl acetate segments into low-density polyethylene, the material has low crystallinity and high melt strength. Polyolefin elastomer (POE) is mainly divided into three types of ethylene / alpha-olefin copolymer, propylene / alpha-olefin copolymer and ethylene-propylene copolymer. POE contains no unsaturated double bond and relatively less tertiary carbon atoms, and has excellent aging resistance. In addition, the relatively narrow molecular weight distribution of POE endows it with good flowability, so that it is not prone to flexing during injection and extrusion processing, thus having good processing and mechanical properties. Low-density polyethylene (LDPE) foamed material and products are widely used in the soft packaging field in the market due to their small density, light weight, large volume, strong energy absorption capacity, good shock absorption, sound insulation and heat insulation performance and other characteristics. However, with the fierce market competition, the resilience requirement of foamed LDPE products is getting higher and higher. At present, the resilience of foamed composite material prepared from LDPE cannot meet the technical requirements, and the melt strength is low and the processability is poor under high shear rate, which limits its application in industry. Therefore, the existing technology generally improves the LDPE foamed material by adding EVA to improve the processing performance and foaming performance of the foamed material.

[0003] A Chinese invention patent with publication number CN118359837B discloses a high-resilience polyolefin foamed material and a preparation method thereof. The preparation of the foamed material includes the following steps: preparation of a polyolefin resin blend, preparation of a thermoplastic elastomer blend, preparation of a foaming precursor, and preparation of a foamed material. The invention prepares a core-shell structure with polyolefin as the core and nano-particles and thermoplastic resin as the shell through mechanical coating and solution casting. The prepared core-shell structure contains porous nano-particles, which can act as a gas diffusion channel during the foaming process, effectively improving the gas diffusion speed. Meanwhile, the porous nano-particles can also play the role of heterogeneous nucleation, effectively reducing the bubble nucleation energy barrier. The core-shell structure will not be damaged during hot pressing and can be well preserved.

[0004] A Chinese invention patent with publication number CN119039651B discloses a preparation method of a wear-resistant modified EVA foamed sole material. Ethylene-vinyl acetate copolymer, POE grafted microcrystalline cellulose, ternary ethylene-propylene rubber, additives, fillers, cross-linking agents and foaming agents are placed in an open mill, mixed and then subjected to mold foaming in a flat vulcanizing machine to obtain the wear-resistant modified EVA foamed sole material.

[0005] Although the existing technology can improve the resilience and wear resistance of the EVA / POE composite foaming material, there are still technical problems that high resilience and flame retardant function are difficult to be considered together, and phase separation is easy to occur by directly adding a flame retardant, so it is necessary to further study the flame retardant composition and structure of the EVA / POE composite foaming material, so as to further improve the foaming performance and resilience performance of the EVA / POE composite foaming material while having the performance of flame retardation. SUMMARY

[0006] The purpose of the present application is to provide an EVA / POE composite high resilience foaming material and a preparation method thereof, which are used to solve the technical problems that high resilience and flame retardant function are difficult to be considered together in the prior art, and phase separation is easy to occur by directly adding a flame retardant.

[0007] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0008] The EVA / POE composite high resilience foaming material comprises the following components by mass fraction: 45-48 parts of EVA, 50-53 parts of POE, 0.2-0.4 parts of a crosslinking agent, 13-18 parts of a foaming agent, 0.8-1.1 parts of a foaming aid, and 4-6 parts of a foaming stabilizer;

[0009] The foaming stabilizer is prepared by mixing a nucleating flame retardant and polydimethylsiloxane at a mass ratio of (5-8):1;

[0010] The nucleating flame retardant is prepared by loading a modified flame retardant on a porous metal framework, and the mass ratio of the porous metal framework to the modified flame retardant is (2-3):(3.2-4.5);

[0011] The modified flame retardant is prepared by grafting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) on 4-terpenol through a carbon-carbon double bond reaction;

[0012] The crosslinking agent is dicumyl peroxide, the foaming agent is azodicarbonamide foaming agent, and the foaming aid is prepared by mixing zinc oxide and zinc stearate at a mass ratio of 1:(2-3).

[0013] The preparation method of the foaming stabilizer comprises the following steps:

[0014] S11, dissolve zinc nitrate in deionized water and then drop it into an aqueous solution of 2-methylimidazole, stir at room temperature, filter, wash and dry to prepare a porous metal framework;

[0015] S12, 4-terpenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) were added into toluene, initiator azobisisobutyronitrile was added, and the reaction was carried out under nitrogen atmosphere, and the modified flame retardant was obtained by filtration, washing and drying; the porous metal frame and the modified flame retardant were added into ethanol, and the nucleation flame retardant was prepared by ultrasonic stirring and rotary evaporation to remove ethanol;

[0016] S13, the nucleation flame retardant and polydimethylsiloxane were mixed to prepare a foaming stabilizer.

[0017] As preferred, the reaction principle of the modified flame retardant is as follows:

[0018]

[0019] The modified flame retardant was analyzed by mass spectrometry, and the results were as follows: m / z: 370.17 (100.0%), 371.17 (23.9%), 372.18 (2.8%).

[0020] As preferred, the amount ratio of zinc nitrate and 2-methylimidazole in S11 is (1.2-1.5) g:(4-8) g, and the stirring speed is 200-300 rpm at room temperature for 1-2 h, and the reaction is carried out for 8-10 h.

[0021] As preferred, the amount ratio of 4-terpenol, DOPO, toluene and azobisisobutyronitrile in S12 is (14-15) g:(20-22) g:(400-500) mL:(0.8-1) g, the reaction is carried out under nitrogen atmosphere at 65-75℃ for 36-48 h, and the modified flame retardant is obtained by centrifugal separation at 10000-12000 rpm for 10-15 min, washing with deionized water and vacuum drying at 50-60℃.

[0022] As preferred, the mass ratio of the porous metal frame and the modified flame retardant in S12 is (2-3):(3.2-4.5), and the ultrasonic stirring power is 300-500 W for 20-40 min.

[0023] The preparation method of EVA / POE composite high-rebound foaming material comprises the following steps:

[0024] S1, ingredient mixing: EVA, POE, crosslinking agent, foaming agent and foaming stabilizer were added into a mixer, mixed at high temperature, and mixed material was prepared by adding a banbury mixer;

[0025] S2, extrusion vulcanization: the mixed material was added into an extruder and extruded at high temperature, and the pre-foaming material was prepared by vulcanization and foaming in a vulcanizing machine;

[0026] S3, secondary foaming: the pre-foaming material is ground to remove the skin, and is pressed into a mold to be secondarily foamed to obtain the EVA / POE composite high-resilience foaming material.

[0027] Preferably, in S1, the temperature is raised to 60-70 DEG C, and mixing and stirring are performed at a speed of 300-500 rpm for 5-10 min, and then the temperature is raised to 90-105 DEG C, and the mixing and stirring are performed for 5-10 min.

[0028] Preferably, in S2, the temperature of each temperature zone of the extruder is set as follows: the temperature of the die head is 130-145 DEG C, the temperature of the first zone is 105-115 DEG C, the temperature of the second zone is 125-135 DEG C, the temperature of the third zone is 135-140 DEG C, the temperature of the fourth zone is 140-150 DEG C, the temperature of the fifth zone is 145-155 DEG C, and the temperature of the sixth zone is 140-150 DEG C.

[0029] Preferably, in S2, the temperature of the vulcanizing machine is 150-165 DEG C, the pressure is 10-20 MPa, and the foaming time is 10-20 min.

[0030] Preferably, in S3, the temperature of the secondary foaming is 160-175 DEG C, and the foaming time is 5-10 min.

[0031] In summary, due to the adoption of the above technical solutions, the present application has the following advantages:

[0032] 1. The EVA / POE composite high-resilience foaming material is prepared by mixing EVA, POE, a foaming agent, a foaming aid, a foaming stabilizer and a cross-linking agent, extruding and vulcanizing, and then secondarily foaming; EVA and POE improve the resilience of the product through a compatibility mechanism; zinc oxide and zinc stearate are used as the foaming aid to increase the gas production speed and the gas production amount; the modified nucleating flame retardant and polydimethylsiloxane are used as the foaming stabilizer to expand the decomposition temperature range of the foaming agent; polydimethylsiloxane reduces the surface tension of the polymer melt, inhibits the coalescence of the cells, the porous metal frame of the modified nucleating flame retardant contains abundant microporous structures, provides a large number of gas nucleation sites, refines the cell size, and makes the distribution more uniform; the material is stable, the melt strength of the foaming matrix material is improved, and thus the resilience is improved.

[0033] 2、The modified nucleation flame retardant of the application is prepared by loading the modified flame retardant on the porous metal framework, the modified flame retardant is prepared by grafting DOPO on 4-terpenol through carbon-carbon double bond reaction, and the cyclic group of the modified flame retardant introduced into 4-terpenol has similar non-polar structure with the EVA / POE matrix material, the compatibility of the modified flame retardant in the EVA / POE material is improved, the phosphorus element in DOPO promotes the formation of carbon layer, and the carbon chain structure of 4-terpenol serves as a supplementary carbon source, thereby enhancing the continuity and strength of the carbon layer; the microporous structure of the porous metal framework provides a loading reaction site, the modified flame retardant is fixed in the micropore by forming hydrogen bonds through intermolecular hydroxyl groups, and the microporous structure has adsorption effect, can reduce the taste of the material by adsorbing formamide generated by the decomposition of the foaming agent, and makes the modified nucleation flame retardant have both bubble nucleation stability and flame retardancy. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0035] The EVA in the application contains 18wt% of acetic acid vinyl and has a density of 0.936g / cm 3 , a melt flow rate of 10g / 10min; the POE is an ethylene / alpha-olefin copolymer, has a density of 0.873g / cm 3 , and a melt flow rate of 1.115g / 10min; the foaming agent is an azodicarbonamide foaming agent, has a decomposition temperature of 165℃, a gas generation amount of 160±5mL / g, and an average particle size of 7μm.

[0036] In the embodiment, the EVA / POE composite high-resilience foaming material is prepared from the following components: 47g of EVA, 53g of POE, 0.3g of dicumyl peroxide crosslinking agent, 15g of azodicarbonamide foaming agent, 0.9g of foaming aid prepared by mixing zinc oxide and zinc stearate at a mass ratio of 1:3, and 5g of foaming stabilizer.

[0037] The preparation method of the foaming stabilizer in the embodiment comprises the following steps:

[0038] S11, dissolve 1.2g of zinc nitrate in 10mL of deionized water, then drop into an aqueous solution prepared by adding 6.7g of 2-methylimidazole to 40mL of deionized water, stir at a speed of 200rpm at room temperature for 1h, stand for 9h, filter, wash and dry, to prepare a porous metal framework;

[0039] S12, 14 g of 4-terpenol and 21 g of DOPO were added into 450 mL of toluene, 0.8 g of initiator azobisisobutyronitrile was added, and the temperature was raised to 65°C under nitrogen atmosphere for 36 h, centrifugal separation was carried out at a speed of 10,000 rpm for 10 min, washed with deionized water, and vacuum dried at 50°C to obtain a modified flame retardant, 2 g of a porous metal frame and 3.2 g of the modified flame retardant were added into 50 mL of ethanol, and ultrasonic stirring was carried out at a power of 300 W for 20 min, and the ethanol was removed by rotary evaporation to obtain a nucleated flame retardant;

[0040] S13, a foaming stabilizer was prepared by mixing 0.8 g of polydimethylsiloxane and 4.2 g of the nucleated flame retardant.

[0041] The preparation method of the EVA / POE composite high-rebound foaming material of the embodiment comprises the following steps:

[0042] S1, batching and mixing: EVA, POE, crosslinking agent, foaming agent and foaming stabilizer were added into a mixer, the temperature was raised to 70°C, and mixing and stirring were carried out at a speed of 300 rpm for 8 min, and a mixer was added to mix at a temperature of 100°C for 5 min to obtain a mixture;

[0043] S2, extrusion and vulcanization: the mixture was added into an extruder, and the temperature of each zone was set as follows: the temperature of the head was 145°C, the temperature of the first zone was 110°C, the temperature of the second zone was 125°C, the temperature of the third zone was 135°C, the temperature of the fourth zone was 145°C, the temperature of the fifth zone was 150°C, and the temperature of the sixth zone was 140°C, and the extruded material was placed into a vulcanizing machine for vulcanization and foaming, the hot pressing temperature of the vulcanizing machine was 165°C, the pressure was 10 MPa, and the foaming time was 10 min to obtain a pre-foaming material;

[0044] S3, secondary foaming: the pre-foaming material was ground to remove the skin, and was pressed into a mold for secondary foaming, the temperature of the secondary foaming was 170°C, and the foaming time was 5 min to obtain an EVA / POE composite high-rebound foaming material.

[0045] In embodiment 2, the EVA / POE composite high-rebound foaming material was prepared from the following components: 45 g of EVA, 50 g of POE, 0.2 g of dicumyl peroxide crosslinking agent, 13 g of azodicarbonamide foaming agent, 0.8 g of foaming aid prepared by mixing zinc oxide and zinc stearate at a mass ratio of 1:2, and 6 g of foaming stabilizer.

[0046] The preparation method of the foaming stabilizer of the embodiment comprises the following steps:

[0047] S11, 1.5 g of zinc nitrate was dissolved in 10 mL of deionized water and then added dropwise to an aqueous solution prepared by adding 4.2 g of 2-methylimidazole to 40 mL of deionized water, stirred at room temperature at a speed of 300 rpm for 1 h, allowed to stand for 10 h, filtered, washed and dried to obtain a porous metal framework;

[0048] S12, 15 g of 4-terpenol and 22 g of DOPO were added to 500 mL of toluene, 1 g of initiator azobisisobutyronitrile was added, and the reaction was carried out at 70°C for 48 h under a nitrogen atmosphere, centrifuged at a speed of 12000 rpm for 10 min, washed with deionized water, and dried at 60°C under vacuum to obtain a modified flame retardant, 2.27 g of the porous metal framework and 3.7 g of the modified flame retardant were added to 50 mL of ethanol, and stirred at a power of 500 W for 20 min, and the ethanol was removed by rotary evaporation to obtain a nucleated flame retardant;

[0049] S13, 1 g of polydimethylsiloxane and 5 g of the nucleated flame retardant were mixed to obtain a foaming stabilizer.

[0050] The preparation method of the EVA / POE composite high-resilience foaming material of the embodiment comprises the following steps:

[0051] S1, batching and mixing: EVA, POE, crosslinking agent, foaming agent and foaming stabilizer were added to a mixer, heated to 60°C and mixed at a speed of 300 rpm for 5 min, and then added to a mixer and mixed at 90°C for 5 min to obtain a mixture;

[0052] S2, extrusion and vulcanization: the mixture was added to an extruder, and the temperature of each zone was set as follows: the temperature of the head was 130°C, the temperature of the first zone was 105°C, the temperature of the second zone was 125°C, the temperature of the third zone was 135°C, the temperature of the fourth zone was 140°C, the temperature of the fifth zone was 145°C, and the temperature of the sixth zone was 140°C. The pre-foaming material was obtained by hot pressing extrusion and vulcanization foaming in a vulcanizing machine, the hot pressing temperature of the vulcanizing machine was 165°C, the pressure was 16 MPa, and the foaming time was 20 min;

[0053] S3, secondary foaming: the pre-foaming material was ground to remove the skin, and then was pressed into a mold for secondary foaming, the temperature of the secondary foaming was 170°C, and the foaming time was 10 min, to obtain the EVA / POE composite high-resilience foaming material.

[0054] In embodiment 3, the EVA / POE composite high-resilience foaming material was prepared from the following components: 45 g of EVA, 53 g of POE, 0.4 g of dicumyl peroxide crosslinking agent, 15 g of azodicarbonamide foaming agent, 1.1 g of foaming aid prepared by mixing zinc oxide and zinc stearate at a mass ratio of 1:3, and 4 g of foaming stabilizer.

[0055] The preparation method of the foaming stabilizer of the embodiment comprises the following steps:

[0056] S11, 1.4 g of zinc nitrate is dissolved in 10 mL of deionized water and then added dropwise into an aqueous solution prepared by adding 5.1 g of 2-methylimidazole into 40 mL of deionized water, stirred at room temperature at a rotation speed of 200 rpm for 1 h, and then left to stand for 9 h. After filtration, washing and drying, a porous metal framework is prepared;

[0057] S12, 14 g of 4-terpenol and 20 g of DOPO are added into 400 mL of toluene, 0.8 g of initiator azobisisobutyronitrile is added, and the mixture is heated to 65°C under a nitrogen atmosphere and reacted for 48 h. After centrifugal separation at a rotation speed of 12000 rpm for 15 min, washing with deionized water and vacuum drying at 50°C, a modified flame retardant is prepared. 3 g of the porous metal framework and 4.5 g of the modified flame retardant are added into 50 mL of ethanol, ultrasonically stirred at a power of 400 W for 30 min, and then the ethanol is removed by rotary evaporation to prepare a nucleated flame retardant;

[0058] S13, 0.75 g of polydimethylsiloxane and 5.25 g of the nucleated flame retardant are mixed to prepare a foaming stabilizer.

[0059] The preparation method of the EVA / POE composite high-rebound foaming material of the embodiment comprises the following steps:

[0060] S1, ingredient mixing: EVA, POE, crosslinking agent, foaming agent and foaming stabilizer are added into a mixer, heated to 65°C, and mixed and stirred at a rotation speed of 300 rpm for 8 min. The mixture is added into a banbury mixer and mixed at 90°C for 10 min to prepare a mixed material;

[0061] S2, extrusion and vulcanization: the mixed material is added into an extruder, and the temperature of each zone is set as follows: the temperature of the head is 140°C, the temperature of the first zone is 115°C, the temperature of the second zone is 130°C, the temperature of the third zone is 135°C, the temperature of the fourth zone is 150°C, the temperature of the fifth zone is 145°C, and the temperature of the sixth zone is 140°C. The extruded material is placed into a vulcanizing machine for vulcanization and foaming, the hot pressing temperature of the vulcanizing machine is 155°C, the pressure is 20 MPa, and the foaming time is 20 min to prepare a pre-foaming material;

[0062] S3, secondary foaming: the pre-foaming material is ground to remove the skin, and then pressed into a mold for secondary foaming. The temperature of the secondary foaming is 160°C, and the foaming time is 5 min to prepare an EVA / POE composite high-rebound foaming material.

[0063] Example 4, the EVA / POE composite high resilience foamed material of the present example is prepared from the following components: 48 g of EVA, 50 g of POE, 0.3 g of dicumyl peroxide crosslinking agent, 17 g of azodicarbonamide foaming agent, 0.8 g of foaming aid prepared by mixing zinc oxide and zinc stearate in a mass ratio of 1:2.5, and 4 g of foaming stabilizer.

[0064] The preparation method of the foaming stabilizer of the present example comprises the following steps:

[0065] S11, 1.3 g of zinc nitrate is dissolved in 10 mL of deionized water and then added dropwise into an aqueous solution prepared by adding 7.2 g of 2-methylimidazole to 40 mL of deionized water, stirring at room temperature at a speed of 250 rpm for 2 h, standing for 10 h, filtering, washing and drying to obtain a porous metal framework;

[0066] S12, 15 g of 4-terpenol and 21 g of DOPO are added to 400 mL of toluene, 1 g of initiator azobisisobutyronitrile is added, and the temperature is raised to 65°C under nitrogen atmosphere for 48 h, centrifugal separation at a speed of 11000 rpm for 10 min, washing with deionized water, and vacuum drying at 55°C to obtain a modified flame retardant, 2.5 g of the porous metal framework and 3.8 g of the modified flame retardant are added to 50 mL of ethanol, ultrasonic stirring at a power of 300 W for 40 min, and rotary evaporation to remove ethanol to obtain a nucleating flame retardant;

[0067] S13, 0.5 g of polydimethylsiloxane and 3.5 g of the nucleating flame retardant are mixed to obtain a foaming stabilizer.

[0068] The preparation method of the EVA / POE composite high resilience foamed material of the present example comprises the following steps:

[0069] S1, batching and mixing: EVA, POE, crosslinking agent, foaming agent and foaming stabilizer are added to a mixer, the temperature is raised to 70°C, and mixing and stirring are carried out at a speed of 500 rpm for 10 min, and then the mixed material is obtained by adding the mixer to a mixing mill and mixing at 105°C for 10 min;

[0070] S2, extrusion and vulcanization: the mixed material is added to an extruder, and the temperature of each zone is set as follows: the temperature of the head is 145°C, the temperature of the first zone is 115°C, the temperature of the second zone is 135°C, the temperature of the third zone is 140°C, the temperature of the fourth zone is 150°C, the temperature of the fifth zone is 155°C, and the temperature of the sixth zone is 150°C; the pre-foamed material is obtained by hot pressing extrusion and placing in a vulcanizing machine for vulcanization and foaming, the hot pressing temperature of the vulcanizing machine is 165°C, the pressure is 20 MPa, and the foaming time is 20 min;

[0071] S3, secondary foaming: the pre-foamed material was ground to remove the skin, and then was pressed into the mold for secondary foaming, the temperature for secondary foaming was 175℃, and the foaming time was 10min, and the EVA / POE composite high resilience foamed material was prepared.

[0072] Comparative Example 1, the difference between this comparative example and Example 1 is that the foaming stabilizer is replaced by talc.

[0073] Comparative Example 2, the difference between this comparative example and Example 1 is that the foaming stabilizer is not added to the modified nucleating flame retardant.

[0074] Comparative Example 3, the difference between this comparative example and Example 1 is that the modified nucleating flame retardant is replaced by a porous metal frame.

[0075] Comparative Example 4, the difference between this comparative example and Example 1 is that no EVA is added.

[0076] Performance test

[0077] The tensile strength and elongation at break of the foamed materials prepared in each example and comparative example were determined according to GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber".

[0078] The impact resilience of the foamed materials prepared in each example and comparative example was determined according to GB / T 1681-2009 "Determination of resilience of vulcanized rubber".

[0079] The limiting oxygen index of the foamed materials prepared in each example and comparative example was determined according to GB / T 2406.2-2021 "Plastics - Determination of the burning behavior in an oxygen index apparatus - Part 2: Room temperature test".

[0080] The formamide content of the foamed materials prepared in each example and comparative example was determined according to GB / T 33390-2016 "Footwear - Determination of limited substances present in footwear and footwear components - Dimethylformamide".

[0081] The test results are shown in Table 1 below:

[0082] Table 1 Performance test results of foamed materials

[0083]

[0084] From the data in the above table, it can be seen that the tensile strength of the high resilience foamed material prepared in Examples 1-4 is 2.7-2.8 MPa, the elongation at break is 270%-276%, and the impact resilience is 18.3%-19.1%, indicating that the high resilience foamed material prepared in the application has excellent impact resilience; the limiting oxygen index of the high resilience foamed material prepared in Examples 1-4 is 27.8%-28.1%, indicating that the high resilience foamed material prepared in the application has excellent flame retardant performance; the formamide content of the high resilience foamed material prepared in Examples 1-4 is 43-46 mg / kg, the formamide content of the comparative example 1 in which the foaming stabilizer is replaced by talc is 123 mg / kg, and the formamide content of the comparative example 2 in which the foaming stabilizer is not added with the modified nucleating flame retardant is 119 mg / kg, further indicating that the high resilience foamed material prepared in the application has excellent odor removal performance.

[0085] The above description is only for the preferred embodiments of the application, but the protection scope of the application is not limited thereto, and any person skilled in the art can make equivalent replacements or changes according to the technical solution and the inventive concept of the application within the technical range disclosed by the application, which should be covered within the protection scope of the application.

[0086] The preferred embodiments of the application disclosed above are only used to help explain the application. The preferred embodiments do not describe all the details and do not limit the application to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the specification. The specification selects and describes these embodiments in order to better explain the principles and practical applications of the application, so that the person skilled in the art can well understand and utilize the application. The application is limited only by the claims and their entire scope and equivalents.

Claims

1. A high resilience foamed material of EVA / POE composite, characterized in that, By mass parts including the following components: 45~48 parts of EVA, 50~53 parts of POE, 0.2~0.4 parts of crosslinking agent, 13~18 parts of foaming agent, 0.8~1.1 parts of foaming aid and 4~6 parts of foaming stabilizer; The foaming stabilizer is prepared by mixing nucleating flame retardant and polydimethylsiloxane in a mass ratio of (5~8):1; The nucleating flame retardant is prepared by loading modified flame retardant on porous metal framework, and the mass ratio of porous metal framework and modified flame retardant is (2~3):(3.2~4.5); The modified flame retardant is prepared by grafting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide on 4-terpenyl alcohol through carbon-carbon double bond reaction; The crosslinking agent is dicumyl peroxide, the foaming agent is azodicarbonamide foaming agent, and the foaming aid is prepared by mixing zinc oxide and zinc stearate in a mass ratio of 1:(2~3); The preparation method of the foaming stabilizer comprises the following steps: S11, dissolve zinc nitrate in deionized water and then drop into the aqueous solution of 2-methyl imidazole, stir at room temperature, filter, wash and dry to prepare porous metal framework; S12, add 4-terpenyl alcohol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into toluene, add initiator azobisisobutyronitrile, heat in nitrogen atmosphere, filter, wash and dry to prepare modified flame retardant, add porous metal framework and modified flame retardant into ethanol, ultrasonic stirring, rotary evaporation to remove ethanol to prepare nucleating flame retardant; S13, mix nucleating flame retardant and polydimethylsiloxane in a mass ratio of (5~8):1 to prepare foaming stabilizer.

2. The EVA / POE compounded high resilience foamed material according to claim 1, characterized in that, In S11, the amount ratio of zinc nitrate and 2-methyl imidazole is (1.2~1.5)g:(4~8)g, stir at room temperature at a speed of 200~300rpm for 1~2h, and stand for 8~10h.

3. The EVA / POE compounded high resilience foamed material according to claim 1, characterized in that, In S12, the amount ratio of 4-terpenyl alcohol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, toluene and azobisisobutyronitrile is (14~15)g:(20~22)g:(400~500)mL:(0.8~1)g, heat to 65~75℃ in nitrogen atmosphere for 36~48h, centrifugal separation at a speed of 10000~12000rpm for 10~15min, wash with deionized water, and vacuum drying at 50~60℃ to prepare modified flame retardant, add porous metal framework and modified flame retardant into ethanol, ultrasonic stirring at a power of 300~500W for 20~40min.

4. The process for the preparation of EVA / POE composite high resilience foamed material according to any one of claims 1-3, characterized in that, Comprise the following steps: S1, batch mixing: add EVA, POE, crosslinking agent, foaming agent and foaming stabilizer into a mixer, heat and mix, add into a banbury mixer to prepare a mixture; S2, extrusion and vulcanization: add the mixture into an extruder to heat and press extrude, put into a vulcanizing machine to vulcanize and foam to prepare a pre-foaming material; S3, secondary foaming: grind the pre-foaming material to remove the skin, press into a mold to foam again to prepare EVA / POE composite high resilience foaming material.

5. The method for preparing the high-resilience foamed material of EVA / POE composite according to claim 4, characterized in that, The temperature in S1 is raised to 60-70 ℃, mixed and stirred at a rotating speed of 300-500 rpm for 5-10 min, and densified at 90-105 ℃ for 5-10 min; the temperature of each temperature zone of the extruder in S2 is set as follows: the temperature of the die head is 130-145 ℃, the temperature of the first zone is 105-115 ℃, the temperature of the second zone is 125-135 ℃, the temperature of the third zone is 135-140 ℃, the temperature of the fourth zone is 140-150 ℃, the temperature of the fifth zone is 145-155 ℃, the temperature of the sixth zone is 140-150 ℃, the temperature of the vulcanizing machine is 150-165 ℃, the pressure is 10-20 MPa, and the foaming time is 10-20 min; the temperature of secondary foaming in S3 is 160-175 ℃, and the foaming time is 5-10 min.

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