WO2023134171A1 - 一种基于eva废弃料的环保发泡材料及eva废弃料的处理方法 - Google Patents

一种基于eva废弃料的环保发泡材料及eva废弃料的处理方法 Download PDF

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WO2023134171A1
WO2023134171A1 PCT/CN2022/114521 CN2022114521W WO2023134171A1 WO 2023134171 A1 WO2023134171 A1 WO 2023134171A1 CN 2022114521 W CN2022114521 W CN 2022114521W WO 2023134171 A1 WO2023134171 A1 WO 2023134171A1
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eva
waste
crushing
banburying
materials
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PCT/CN2022/114521
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English (en)
French (fr)
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卢鑫
廖毅彬
王育玲
林志杰
丁思博
丁思恩
许春树
林臭知
代雪玲
郑荣大
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茂泰(福建)鞋材有限公司
盛泰(福建)鞋材有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B29B2017/0424—Specific disintegrating techniques; devices therefor
    • B29B2017/0476—Cutting or tearing members, e.g. spiked or toothed cylinders or intermeshing rollers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention belongs to the technical field of organic polymer compounds, and in particular relates to a foaming material for shoes based on EVA waste material and a treatment method for EVA waste material.
  • EVA Ethylene-vinyl acetate copolymer
  • the content of vinyl acetate (VA) is 5%-40%.
  • PE polyethylene
  • EVA reduces high crystallinity and improves toughness and impact resistance due to the introduction of vinyl acetate monomer into the molecular chain.
  • filler compatibility and heat sealing performance are widely used in foamed shoe materials, functional shed films, packaging molds, hot melt adhesives, wires and cables and toys and other fields.
  • EVA Due to its toughness, foamability and good molding properties, EVA has been widely used in mid-to-high-end slippers and shoe soles.
  • EVA plastics are used to make slippers or soles by injection molding process. Injection molding is to heat and melt the raw materials into a turbulent state by the injection equipment, and then inject turbulent EVA plastic raw materials from the injection machine to the feed nozzle of the mold. Due to the process, mold structure, etc., there will be waste materials such as scraps and defective products in the production process. Due to the composition of EVA plastic itself and the processing technology of raw materials, the EVA material has undergone chemical crosslinking reaction. Manufacturers of end products cannot reuse these waste materials.
  • EVA waste After a small amount of EVA waste is ground into powder, it will be added to low-grade EVA products in a small amount; for these waste materials, traditional methods are generally landfilled with other waste or entered into waste. Incineration power generation in power plants, etc. However, in terms of the market price of its raw materials, if these waste materials can be recycled, they still have considerable utilization value. Burying and burning is a huge waste of resources and needs further improvement.
  • the purpose of the present invention is to overcome the shortcoming of prior art, provide a kind of treatment method of EVA waste material, another purpose is to provide a kind of environmental protection foaming material prepared based on the EVA recovery film after the above-mentioned method treatment.
  • the present invention adopts following technical scheme:
  • a processing method for EVA waste material comprising the following steps:
  • Step 1 Crushing waste products such as waste EVA soles, waste EVA sheets, and waste EVA scraps to obtain blocky crushed materials with a length less than 7cm and a width of less than 5cm; then put the blocky crushed materials into the waste crusher to obtain strip-shaped crushed materials material;
  • waste products such as waste EVA soles, waste EVA sheets, and waste EVA scraps
  • Step 2 Put the strip-shaped crushed material, sarin resin, and PMP obtained in step 1 into the internal mixer at a weight ratio of 85:4-10:4-8, and gradually increase the mixing temperature to a maximum temperature of 150°C.
  • the refining time is 18-25min, and block-shaped banburying material is obtained;
  • Step 3 processing the block-shaped banburying material after banburying through a screw extruder and an open mill to obtain an EVA recovery film;
  • the waste crusher includes a crushing assembly for crushing EVA waste, the crushing assembly includes a first crushing roller and a second crushing roller oppositely arranged, and a pair of EVA waste is formed between the first crushing roller and the second crushing roller.
  • the broken crushing channel, the surface of the first crushing roller is a smooth surface, the surface of the second crushing roller is provided with a plurality of crushing grooves, and the gap between the first crushing roller and the second crushing roller is less than 3mm.
  • the crushing groove is obliquely arranged on the surface of the second crushing roller, and the inclination angle is 10-45°.
  • the crushing groove has a structure with a large top and a small bottom along the radial direction.
  • the PMP is a fatty acid oligomer.
  • the base temperature of the screw extruder is 130-150°C.
  • the specific operation of the mill is as follows: the temperature is lower than 65°C and the rolling is formed into a film.
  • the thickness of the recycled EVA film is less than or equal to 0.02mm.
  • a kind of environmental protection foaming material based on EVA waste material is made up of the raw material of following weight part;
  • the preparation method includes the following steps: First, mix other raw materials except the crosslinking agent BIBP and the foaming agent AC evenly before banburying, adjust the banburying temperature to 86-91°C, keep it for 4 minutes, and then turn the material ; When the banburying temperature rises to 95°C, turn the material for the second time; when the banburying temperature rises to 101°C, turn the material for the third time, and add crosslinking agent BIBP and foaming agent AC, and wait for the banburying temperature to rise to 107°C °C, the fourth turning; when the banburying temperature rises to 112°C, turn the fifth time, and then banburying for 1 minute, and finally pouring, kneading, and granulation to obtain environmentally friendly foaming rice, which is molded and foamed Get environmentally friendly foam materials.
  • biodegradation agent is a polyolefin graft modification product.
  • the present invention realizes the resource recovery and reuse of EVA shoe sole heads, defective products, waste products and leftovers by limiting the specific treatment methods of EVA waste materials, and alleviates the environmental problems caused by white pollution, and after crushing, banburying,
  • the content of acetophenone and 2-phenyl-2-propanol in the recovered EVA film obtained by refining treatment is less than 20mg/kg, which meets the REACH regulations and the environmental protection requirements of "Zero Discharge of Hazardous Chemical Substances" (ZDHC), and meets the requirements of international brands environmental protection requirements;
  • the block material is crushed and crushed by shear force, and the foaming gas in the foamed EVA can be driven out to obtain a strip-shaped crushed material;
  • the waste EVA material is a foaming material, which is light in weight and has a shallow pattern on the surface; in addition, the waste EVA sole with good wear resistance has a high content of wear-resistant agent and a smooth surface. If the waste EVA sole is injection-molded at one time, the surface also contains more mold release agents, resulting in a smooth surface of the waste EVA sole. Therefore, the present invention applies for setting a crushing groove, and the EVA waste is brought in through the crushing groove, which can improve the crushing efficiency;
  • PMP is a fatty acid oligomer, which can improve the dispersion of the rubber compound, improve the fluidity of the rubber compound, facilitate better shearing in the internal mixer, and better disperse the sarin resin;
  • Sarin resin is a material with high viscosity, easy crystallization and good toughness, which is conducive to the viscosity increase and blending of materials, and can also improve the tensile strength of the rear section. Cloth performance, not easy to break;
  • the screw extruder can make the mixed material more uniform and improve the toughness of the material after banburying. At the same time, it can also decompose the residual crosslinking agent and discharge volatile organic compounds.
  • Fig. 1 is the structural representation of crushing assembly
  • Fig. 2 is the structural representation of the second crushing roller
  • a processing method for EVA waste material comprising the following steps:
  • Step 1 put waste EVA soles, waste EVA sheets, waste EVA scraps and other waste products into the crusher, and crush them to obtain blocky crushed materials with a length less than 7cm and a width of less than 5cm; then put the blocky crushed materials into the waste crusher , to obtain strip-shaped crushed material;
  • Step 2 Put the strip-shaped crushed material, sarin resin, and PMP obtained in step 1 into the internal mixer at a weight ratio of 85:4-10:4-8, and gradually increase the mixing temperature to a maximum temperature of 150°C.
  • the refining time is 18-25min, and block-shaped banburying material is obtained;
  • Step 3 the bulk banbury after banburying is processed through screw extruder, open mill, to obtain EVA recovery film;
  • the waste crusher includes a crushing assembly for crushing EVA waste, the crushing assembly includes a first crushing roller and a second crushing roller oppositely arranged, and a pair of EVA waste is formed between the first crushing roller and the second crushing roller.
  • Broken crushing channel the surface of the first crushing roller is smooth, and the surface of the second crushing roller is provided with multiple crushing grooves; the gap between the first crushing roller and the second crushing roller is less than 3mm; the crushing grooves are set obliquely at On the surface of the second crushing roller, the inclination angle is 10-45°, and the inclination angle is preferably 30°; specifically, the crushing grooves have a structure with a large top and a small bottom along the radial direction; the gap between two adjacent crushing grooves is 3-50mm , the width of the groove is 1-4mm, the depth is 0.3-3mm, the groove is trapezoidal, and the short side of the trapezoid is 0.1-0.8mm; further, the waste crusher is equipped with a high-power waste gas collection device to collect the ammoni
  • the thickness of the EVA recycling film is less than or equal to 0.02mm, and the PMP is a fatty acid oligomer.
  • step 1 after the broken strips come out, they are spread out on the ground, spread out, and do not accumulate, which is conducive to heat dissipation and air dissipation.
  • step 2 the material chamber of the internal mixer is airtight. During operation, the chamber is under negative pressure, and there are suction pipes around the chamber, through which volatile organic compounds are sucked away by the gas collecting device.
  • step 3 the base temperature of the screw extruder is 130-150°C; the material poured out of the internal mixer will still be a little loose. Extruding through the screw can make the material more uniform, improve the toughness of the material, and at the same time remove the residual The cross-linking agent decomposes and discharges volatile organic compounds.
  • the specific operation of the mill is as follows: the temperature is lower than 65°C and the film is rolled into a film.
  • a kind of environmental protection foaming material based on EVA waste material is made up of the raw material of following weight part;
  • Its preparation method comprises the following steps: First mix other raw materials except the cross-linking agent BIBP and foaming agent AC evenly, then carry out banburying, adjust the banburying temperature to be controlled at 86-91° C., keep for 4 minutes and then turn the material; The mixing temperature rises to 95°C, and the material is turned for the second time; when the banburying temperature rises to 101°C, the material is turned for the third time, and the cross-linking agent BIBP and foaming agent AC are added, and when the banburying temperature rises to 107°C, the second time Turn the material four times; when the mixing temperature rises to 112°C, turn the material for the fifth time, and then banbury for 1 minute, and finally pour the material, start refining, and granulate to obtain environmentally friendly foam rice, which is molded and foamed to produce environmentally friendly foam. bubble material.
  • SEBS is oil-free granular and has excellent toughening effect.
  • the biodegradation agent is a polyolefin graft modification product.
  • the biodegradation agent can accelerate the degradation rate of the polymer in an anaerobic environment.
  • the rubber sole can be degraded by at least 90% after 90 days of anaerobic landfill; specifically, biodegradation
  • the agent is made of polyolefin material injected with anaerobic organic additives.
  • the biodegradant attracts natural microorganisms and produces enzymes to destroy rubber polymers.
  • Microorganisms obtain the energy they need by digesting rubber, accelerate the reproduction speed of microorganisms, increase the biodegradation rate, and finally reduce rubber products to organic decay (organic humus).
  • a processing method for EVA waste material comprising the following steps:
  • Step 1 put waste EVA soles, waste EVA sheets, waste EVA scraps and other waste products into the crusher, and crush them to obtain blocky crushed materials with a length less than 7cm and a width of less than 5cm; then put the blocky crushed materials into the waste crusher , to obtain strip-shaped crushed material;
  • Step 2 Put the strip-shaped crushed material, sarin resin, and PMP obtained in step 1 into the internal mixer at a weight ratio of 85:4:8, and gradually increase the mixing temperature to a maximum temperature of 150°C, and the mixing time is 18 minutes. Obtain block banbury;
  • Step 3 processing the block-shaped banburying material after banburying through a screw extruder and an open mill to obtain an EVA recovery film;
  • the crusher includes a crushing assembly for crushing the EVA waste material.
  • the crushing assembly includes a first crushing roller and a second crushing roller that are oppositely arranged.
  • the surface of the first crushing roller is smooth, and the surface of the second crushing roller is provided with multiple crushing grooves; the gap between the first crushing roller and the second crushing roller is 1.5-2 mm; specifically, the crushing grooves are set obliquely On the surface of the second crushing roller, the inclination angle is 15°; furthermore, the crushing groove has a structure with a large top and a small bottom along the radial direction, the gap between the crushing grooves is 12mm, the width of the crushing groove is 2mm, and the depth is 1.5mm.
  • the groove is trapezoidal, and the short side of the trapezoid is 0.5mm.
  • the thickness of the EVA recycling film is 0.02mm, and the PMP is a fatty acid oligomer.
  • the base temperature of the screw extruder is 130°C; the specific operation of the mill is as follows: the temperature is lower than 65°C to form a film by calendering.
  • a kind of environmental protection foaming material based on EVA waste material is made up of the raw material of following weight part;
  • Its preparation method comprises the following steps: First mix other raw materials except the cross-linking agent BIBP and foaming agent AC evenly, then carry out banburying, adjust the banburying temperature to be controlled at 86-91° C., keep for 4 minutes and then turn the material; The mixing temperature rises to 95°C, and the material is turned for the second time; when the banburying temperature rises to 101°C, the material is turned for the third time, and the cross-linking agent BIBP and foaming agent AC are added, and when the banburying temperature rises to 107°C, the second time Turn the material four times; when the mixing temperature rises to 112°C, turn the material for the fifth time, and then banbury for 1 minute, and finally pour the material, start refining, and granulate to obtain environmentally friendly foam rice, which is molded and foamed to produce environmentally friendly foam. bubble material.
  • the environmentally friendly foam material can degrade 92% (mass ratio) after 90 days of anaerobic landfill.
  • the degradation experiment refers to GB/T 33797, and the mass loss is calculated after 90 days of landfill.
  • a processing method for EVA waste material comprising the following steps:
  • Step 1 put waste EVA soles, waste EVA sheets, waste EVA scraps and other waste products into the crusher, and crush them to obtain blocky crushed materials with a length less than 7cm and a width of less than 5cm; then put the blocky crushed materials into the waste crusher , to obtain strip-shaped crushed material;
  • Step 2 Put the strip-shaped crushed material, sarin resin, and PMP obtained in step 1 into the internal mixer at a weight ratio of 85:10:4, and gradually increase the mixing temperature to a maximum temperature of 150°C, and the mixing time is 25 minutes. Obtain block banbury;
  • Step 3 processing the block-shaped banburying material after banburying through a screw extruder and an open mill to obtain an EVA recovery film;
  • the crusher includes a crushing assembly for crushing the EVA waste material.
  • the crushing assembly includes a first crushing roller and a second crushing roller that are oppositely arranged. crushing channel, the surface of the first crushing roller is smooth, and the surface of the second crushing roller is provided with multiple crushing grooves; the gap between the first crushing roller and the second crushing roller is 1.5-2mm; specifically, the crushing grooves
  • the groove is obliquely arranged on the surface of the second crushing roller, and the inclination angle is 15°; further, the crushing groove has a structure of large up and down in the radial direction, the gap between the crushing grooves is 30mm, the width of the groove is 3mm, and the depth is 3mm.
  • the groove is trapezoidal, and the short side of the trapezoid is 0.8mm.
  • the thickness of the EVA recycling film is 0.01mm, and the PMP is a fatty acid oligomer.
  • step 3 the base temperature of the screw extruder is 150°C; the specific operation of the mill is: the temperature is lower than 65°C to form a film by calendering.
  • a kind of environmental protection foaming material based on EVA waste material is made up of the raw material of following weight part;
  • Its preparation method comprises the following steps: First mix other raw materials except the cross-linking agent BIBP and foaming agent AC evenly, then carry out banburying, adjust the banburying temperature to be controlled at 86-91° C., keep for 4 minutes and then turn the material; The mixing temperature rises to 95°C, and the material is turned for the second time; when the banburying temperature rises to 101°C, the material is turned for the third time, and the cross-linking agent BIBP and foaming agent AC are added, and when the banburying temperature rises to 107°C, the second time Turn the material four times; when the mixing temperature rises to 112°C, turn the material for the fifth time, and then banbury for 1 minute, and finally pour the material, start refining, and granulate to obtain environmentally friendly foam rice, which is molded and foamed to produce environmentally friendly foam. bubble material.
  • the environmentally friendly foam material can degrade 85% (mass ratio) after 90 days of anaerobic landfill.
  • the degradation experiment refers to GB/T 33797, and the mass loss is calculated after 90 days of landfill.
  • a processing method for EVA waste material comprising the following steps:
  • Step 1 put waste EVA soles, waste EVA sheets, waste EVA scraps and other waste products into the crusher, and crush them to obtain blocky crushed materials with a length less than 7cm and a width of less than 5cm; then put the blocky crushed materials into the waste crusher , to obtain strip-shaped crushed material;
  • Step 2 Put the strip-shaped crushed material, sarin resin, and PMP obtained in step 1 into the internal mixer at a weight ratio of 85:7:6, and gradually increase the mixing temperature to a maximum temperature of 150°C, and the mixing time is 21 minutes. Obtain block banbury;
  • Step 3 processing the block-shaped banburying material after banburying through a screw extruder and an open mill to obtain an EVA recovery film;
  • the crusher includes a crushing assembly for crushing the EVA waste material.
  • the crushing assembly includes a first crushing roller and a second crushing roller that are oppositely arranged.
  • the crushing channel, the surface of the first crushing roller is a smooth surface, and the surface of the second crushing roller is provided with a plurality of crushing grooves; the gap between the first crushing roller and the second crushing roller is less than 3mm; specifically, the crushing grooves are set obliquely at the 2.
  • the inclination angle is 15°; furthermore, the crushing groove has a large upper and a smaller structure along the radial direction, the gap between the crushing grooves is 8mm, the width of the groove is 1mm, and the depth is 0.3mm, and the groove is trapezoidal , the short side of the trapezoid is 0.1mm.
  • the thickness of the EVA recycling film is 0.008mm, and the PMP is a fatty acid oligomer.
  • the base temperature of the screw extruder is 140°C; the specific operation of the mill is as follows: the temperature is lower than 65°C and the film is formed by calendering.
  • a kind of environmental protection foaming material based on EVA waste material is made up of the raw material of following weight part;
  • Its preparation method comprises the following steps: First mix other raw materials except the cross-linking agent BIBP and foaming agent AC evenly, then carry out banburying, adjust the banburying temperature to be controlled at 86-91° C., keep for 4 minutes and then turn the material; The mixing temperature rises to 95°C, and the material is turned for the second time; when the banburying temperature rises to 101°C, the material is turned for the third time, and the cross-linking agent BIBP and foaming agent AC are added, and when the banburying temperature rises to 107°C, the second time Turn the material four times; when the mixing temperature rises to 112°C, turn the material for the fifth time, and then banbury for 1 minute, and finally pour the material, start refining, and granulate to obtain environmentally friendly foam rice, which is molded and foamed to produce environmentally friendly foam. bubble material.
  • the environmentally friendly foam material can degrade 94% (mass ratio) after 90 days of anaerobic landfill.
  • the degradation experiment refers to GB/T 33797, and the mass loss is calculated after 90 days of landfill.
  • Embodiment 1 to embodiment 3 and comparative example are carried out corresponding test, obtain following data:
  • the compression deformation test refers to HG/T2876 (temperature 50 °C, time 6 hours, compression ratio 50%)
  • the rebound rate test adopts GT-7042-VAA vertical elasticity testing machine
  • the content of propanol is extracted by acetone and then analyzed by GCMS (detection limit 2mg/kg) after the sole is left open at room temperature for 24 hours.
  • the environmental protection foaming material prepared by the present application has a small compression deformation rate and high resilience, which meets the needs of the sole; and the acetophenone and 2-
  • the content of phenyl-2-propanol is less than 20mg/kg, which complies with the REACH regulations and the environmental protection requirements of "Zero Discharge of Hazardous Chemical Substances” (ZDHC), as well as the environmental protection requirements of international brands.
  • the invention discloses an environmentally friendly foaming material based on EVA waste materials and a treatment method for EVA waste materials.
  • the treatment method includes the following steps: step 1, waste materials such as waste EVA soles, waste EVA sheets, and waste EVA scraps are crushed to obtain Strip crushed material; step 2, the strip crushed material, sarin resin, and PMP obtained in step 1 are put into the internal mixer in a ratio of 85:4-10:4-8 by weight, and the banburying temperature rises gradually, the highest The temperature is 150°C, the banburying time is 18-25min, and block banbury is obtained; step 3, the block banbury after banbury is processed by screw extruder and open mill to obtain EVA recovery film;
  • the invention realizes the resource recovery and reuse of EVA shoe sole materials, defective products, waste products and scraps by limiting the specific treatment methods of EVA waste materials, and alleviates the environmental problems caused by white pollution.
  • the processed EVA waste materials are used in the preparation of shoe soles , The addition ratio can be increased to more than 70%, which

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Abstract

一种基于EVA废弃料的环保发泡材料及EVA废弃料的处理方法，处理方法包括以下步骤：步骤一，将废EVA鞋底、废EVA片材、废EVA边角料等废弃料破碎得到条状破碎料；步骤二，将步骤一得到的条状破碎料、沙林树脂、PMP按重量比85:4-10:4-8的比例投入密炼机中，密炼温度逐渐上升，最高温度150℃，密炼时间18-25min，得块状密炼料；步骤三，将密炼后的块状密炼料经螺杆挤出机、开炼机进行处理，以得到EVA回收膜；本发明通过限定EVA废弃料的具体处理方式，实现对EVA鞋底料头、次品、废品和边角料的资源回收再利用，缓解白色污染带来的环境问题，经过处理后的EVA废弃料在鞋底制备中，添加比例可增加到70％以上，大大减少资源的浪费，提高废弃料的利用率。

Description

一种基于EVA废弃料的环保发泡材料及EVA废弃料的处理方法 技术领域
本发明属于有机高分子化合物技术领域，具体涉及一种基于EVA废弃料的鞋用发泡材料及EVA废弃料的处理方法。
背景技术
乙烯-醋酸乙烯共聚物，简称EVA。一般醋酸乙烯(VA)的含量在5％-40％，与聚乙烯(PE)相比，EVA由于在分子链中引入醋酸乙烯单体，从而降低了高结晶度，提高了韧性、抗冲击性、填料相溶性和热密封性能，被广泛用于发泡鞋材、功能性棚膜、包装模、热熔胶、电线电缆及玩具等领域。
由于EVA具有韧性、可发泡和良好的成型性能，在中高端拖鞋、鞋底的应用已非常普遍。EVA塑料制作拖鞋或鞋底时采用的都是注射成型工艺，注射成型是由射出设备将原料加温熔解为紊流态后，由射出机向模具的进料嘴注射紊流态的EVA塑料原料。由于工艺、模具结构等等原因，生产过程中会有如料头、残次品等废弃料，这些废弃料由于EVA塑料本身成分、原料加工工艺等的原因，EVA材料已发生化学交联反应，作为终端制品的制造企业无法对这些废弃料进行再利用，少量EVA废弃料磨成粉末后，会被少量添加到低档EVA产品中；对于这些废弃料，传统的做法一般和其他垃圾填埋或进入垃圾发电厂焚烧发电等。然而就其原料的市场价格而言，这些废弃料如果能够再生利用，还是有相当的利用价值的，一埋一烧了之是一种极大的资源浪费，有待进一步改进。
发明内容
本发明的目的是克服现有技术的缺点，提供一种EVA废弃料的处理方法，另一目的是提供一种基于上述方法处理后的EVA回收膜制备的环保发泡材料。
本发明采用如下技术方案：
一种EVA废弃料的处理方法，包括以下步骤：
步骤一，将废EVA鞋底、废EVA片材、废EVA边角料等废品破碎得到长度低于7cm，宽度小于5cm的块状破碎料；再将块状破碎料投入废料破碎机中，得到条状破碎料；
步骤二，将步骤一得到的条状破碎料、沙林树脂、PMP按重量比85:4-10:4-8的比例投入密炼机中，密炼温度逐渐上升，最高温度150℃，密炼时间18-25min，得块状密炼料；
步骤三，将密炼后的块状密炼料经螺杆挤出机、开炼机进行处理，以得到EVA回收膜；
所述废料破碎机包括用于对EVA废弃料进行破碎的破碎组件，破碎组件包括相对设置的第一破碎辊及第二破碎辊，第一破碎辊与第二破碎辊之间形成对EVA废弃料破碎的破碎通道，第一破碎辊表面为光滑面，第二破碎辊表面开设有多个破碎凹槽，第一破碎辊与第二破碎辊之间的辊隙小于3mm。
进一步的，所述破碎凹槽倾斜设置在第二破碎辊表面，倾斜角度为10-45°。
进一步的，所述破碎凹槽沿径向呈上大下小的结构。
进一步的，所述PMP为脂肪酸类低聚物。
进一步的，所述步骤三中，螺杆挤出机的基础温度为130-150℃。
进一步的，所述步骤三中，开炼机具体操作为：温度低于65℃压延成膜。
进一步的，所述EVA回收膜的厚度小于或等于0.02mm。
一种基于EVA废弃料的环保发泡材料，由以下重量份的原料组成；
Figure PCTCN2022114521-appb-000001
进一步的，其制备方法包括以下步骤：先将除交联剂BIBP和发泡剂AC之外的其他原料混合均匀后进行密炼，调整密炼温度控制为86-91℃，保持4min后翻料；待密炼温度升至95℃，第二次翻料；待密炼温度升至101℃，第三次翻料，并加入交联剂BIBP和发泡剂AC，待密炼温度升至107℃，第四次翻料；待密炼温度升至112℃，第五次翻料，再密炼1min，最后倒料、开炼、造粒，得到环保发泡料米，经模压发泡制得环保发泡 材料。
进一步的，所述生物降解剂是聚烯烃接枝改性产物。
由上述对本发明的描述可知，与现有技术相比，本发明的有益效果是：
第一，本发明通过限定EVA废弃料的具体处理方式，实现对EVA鞋底料头、次品、废品和边角料的资源回收再利用，缓解白色污染带来的环境问题，且经过破碎、密炼、开炼处理得到的EVA回收膜中苯乙酮和2-苯基-2-丙醇含量均小于20mg/kg，符合REACH法规和“有害化学物质零排放”(ZDHC)的环保要求，符合国际品牌的环保要求；
第二，沙林树脂、PMP与废EVA鞋底破碎料一起密炼，有效改善废EVA鞋底破碎料的相粘性和流动性，显著提升其加工性能，在EVA鞋底中添加比例可达到79％(质量比)，大大减少资源的浪费，提高废弃料的利用率
第三，通过限定废料破碎机中破碎组件的结构及辊隙，通过剪切力将块状材料碾压破碎，且能将发泡EVA中的发泡气体赶出，得到条状破碎料；
第四，第二破碎辊表面设置有破碎凹槽，因为EVA废弃料是发泡材料，质量轻，而且表面花纹浅；另外，耐磨好的废EVA鞋底，耐磨剂含量高，表面光滑，若是一次射出成型的废EVA鞋底，表面还含较多脱模剂，导致废EVA鞋底表面光滑，所以本发明申请设置破碎凹槽，通过破碎凹槽带入EVA废弃料，能提高破碎效率；
第五，PMP为脂肪酸类低聚物，可改善胶料的分散性，提高胶料的流动性，有利于密炼机中更好地剪切，让沙林树脂更好地分散；
第六，采用沙林树脂与破碎后的废弃EVA破碎料配合，沙林树脂是粘度大、易结晶、韧性好的材料，有利于材料之间的增粘、共混，又能提升后段拉布性能，不容易断；
第七，密炼后的密炼料经螺杆挤出机，可以让料更均匀，提高材料韧性，同时也可以将残余的交联剂分解，并排出可挥发性有机物。
附图说明
图1为破碎组件的结构示意图；
图2为第二破碎辊的结构示意图；
图中，1-第一破碎辊、2-第二破碎辊、21-破碎凹槽。
具体实施方式
以下通过具体实施方式对本发明作进一步的描述。
一种EVA废弃料的处理方法，包括以下步骤：
步骤一，将废EVA鞋底、废EVA片材、废EVA边角料等废品投入破碎机中，破碎得到长度低于7cm，宽度小于5cm的块状破碎料；再将块状破碎料投入废料破碎机中，得到条状破碎料；
步骤二，将步骤一得到的条状破碎料、沙林树脂、PMP按重量比85:4-10:4-8的比例投入密炼机中，密炼温度逐渐上升，最高温度150℃，密炼时间18-25min，得块状密炼料；
步骤三，将密炼后的块状密炼料经螺杆挤出机、开炼机进行处理， 以得到EVA回收膜；
其中，废料破碎机包括用于对EVA废弃料进行破碎的破碎组件，破碎组件包括相对设置的第一破碎辊及第二破碎辊，第一破碎辊与第二破碎辊之间形成对EVA废弃料破碎的破碎通道，第一破碎辊表面为光滑面，第二破碎辊表面开设有多个破碎凹槽；第一破碎辊与第二破碎辊之间的辊隙小于3mm；破碎凹槽倾斜设置在第二破碎辊表面，倾斜角度为10-45°，优选倾斜角度为30°；具体的，破碎凹槽沿径向呈上大下小的结构；相邻两破碎凹槽的间隙是3-50mm，凹槽的宽度1-4mm、深度0.3-3mm，凹槽成梯形，梯形短边是0.1-0.8mm；进一步的，废料破碎机上设置有大功率废气收集装置，收集破碎过程中挥发出来的氨气、苯乙酮、2P-2P、二甲酰胺等可挥发性有机物。
EVA回收膜的厚度小于或等于0.02mm，PMP为脂肪酸类低聚物。
步骤一中，条状破碎料出来后，摊开铺在地上，散开，不堆积，有利于散热和散气。
步骤二中，密炼机的料腔是密闭的，运行过程中，腔体内是负压，且在腔体四周有吸气管，可挥发性有机物通过吸气管被集气装置抽走。
步骤三中，螺杆挤出机的基础温度为130-150℃；密炼机倒出的料，还会有点松散，经过螺杆挤出，可以让料更均匀，提高材料韧性，同时也可以将残余的交联剂分解，并排出可挥发性有机物。
开炼机具体操作为：温度低于65℃压延成膜。
一种基于EVA废弃料的环保发泡材料，由以下重量份的原料组成；
Figure PCTCN2022114521-appb-000002
其制备方法包括以下步骤：先将除交联剂BIBP和发泡剂AC之外的其他原料混合均匀后进行密炼，调整密炼温度控制为86-91℃，保持4min后翻料；待密炼温度升至95℃，第二次翻料；待密炼温度升至101℃，第三次翻料，并加入交联剂BIBP和发泡剂AC，待密炼温度升至107℃，第四次翻料；待密炼温度升至112℃，第五次翻料，再密炼1min，最后倒料、开炼、造粒，得到环保发泡料米，经模压发泡制得环保发泡材料。
其中，SEBS是不含油的颗粒状，具有优异的增韧效果。
生物降解剂是聚烯烃接枝改性产物，生物降解剂能加速聚合物在厌氧环境下的降解速度，橡胶鞋底可实现90天厌氧填埋后，降解至少90％；具体的，生物降解剂是由聚烯烃材料注入厌氧有机助剂制成，在充满活性厌氧生物的填埋场中(垃圾填埋场和深海)，生物降解剂吸引自然界微 生物，并产生酶，破坏橡胶高分子结构，微生物通过消化橡胶得到所需要的能量，并加速微生物的繁殖速度，提升生物降解速率，让橡胶产品最后还原成有机腐化物(有机腐殖质)。
实施例1
一种EVA废弃料的处理方法，包括以下步骤：
步骤一，将废EVA鞋底、废EVA片材、废EVA边角料等废品投入破碎机中，破碎得到长度低于7cm，宽度小于5cm的块状破碎料；再将块状破碎料投入废料破碎机中，得到条状破碎料；
步骤二，将步骤一得到的条状破碎料、沙林树脂、PMP按重量比85:4:8的比例投入密炼机中，密炼温度逐渐上升，最高温度150℃，密炼时间18min，得块状密炼料；
步骤三，将密炼后的块状密炼料经螺杆挤出机、开炼机进行处理，以得到EVA回收膜；
其中，破碎机包括用于对EVA废弃料进行破碎的破碎组件，破碎组件包括相对设置的第一破碎辊及第二破碎辊，第一破碎辊与第二破碎辊之间形成对EVA废弃料破碎的破碎通道，第一破碎辊表面为光滑面，第二破碎辊表面开设有多个破碎凹槽；第一破碎辊与第二破碎辊的间隙为1.5-2mm；具体的，破碎凹槽倾斜设置在第二破碎辊表面，倾斜角度为15°；进一步的，破碎凹槽沿径向呈上大下小的结构，破碎凹槽的间隙是12mm，破碎凹槽的宽度2mm、深度1.5mm，破碎凹槽成梯形，梯形短边 是0.5mm。
EVA回收膜的厚度为0.02mm，PMP为脂肪酸类低聚物。
步骤三中，螺杆挤出机的基础温度为130℃；开炼机具体操作为：温度低于65℃压延成膜。
一种基于EVA废弃料的环保发泡材料，由以下重量份的原料组成；
Figure PCTCN2022114521-appb-000003
其制备方法包括以下步骤：先将除交联剂BIBP和发泡剂AC之外的其他原料混合均匀后进行密炼，调整密炼温度控制为86-91℃，保持4min后翻料；待密炼温度升至95℃，第二次翻料；待密炼温度升至101℃，第三次翻料，并加入交联剂BIBP和发泡剂AC，待密炼温度升至107℃，第四次翻料；待密炼温度升至112℃，第五次翻料，再密炼1min，最后倒料、开炼、造粒，得到环保发泡料米，经模压发泡制得环保发泡材料。
环保发泡材料可实现90天厌氧填埋后，降解92％(质量比)。降解实 验参考GB/T 33797，填埋90天后，计算质量损失。
实施例2
一种EVA废弃料的处理方法，包括以下步骤：
步骤一，将废EVA鞋底、废EVA片材、废EVA边角料等废品投入破碎机中，破碎得到长度低于7cm，宽度小于5cm的块状破碎料；再将块状破碎料投入废料破碎机中，得到条状破碎料；
步骤二，将步骤一得到的条状破碎料、沙林树脂、PMP按重量比85:10:4的比例投入密炼机中，密炼温度逐渐上升，最高温度150℃，密炼时间25min，得块状密炼料；
步骤三，将密炼后的块状密炼料经螺杆挤出机、开炼机进行处理，以得到EVA回收膜；
其中，破碎机包括用于对EVA废弃料进行破碎的破碎组件，破碎组件包括相对设置的第一破碎辊及第二破碎辊，第一破碎辊与第二破碎辊之间形成对EVA废弃料破碎的破碎通道，第一破碎辊表面为光滑面，第二破碎辊表面开设有多个破碎凹槽；第一破碎辊与第二破碎辊之间的辊隙为1.5-2mm；具体的，破碎凹槽倾斜设置在第二破碎辊表面，倾斜角度为15°；进一步的，破碎凹槽沿径向呈上大下小的结构，破碎凹槽的间隙是30mm，凹槽的宽度3mm、深度3mm，凹槽成梯形，梯形短边是0.8mm。
EVA回收膜的厚度为0.01mm，PMP为脂肪酸类低聚物。
步骤三中，螺杆挤出机的基础温度为150℃；开炼机具体操作为：温 度低于65℃压延成膜。
一种基于EVA废弃料的环保发泡材料，由以下重量份的原料组成；
Figure PCTCN2022114521-appb-000004
其制备方法包括以下步骤：先将除交联剂BIBP和发泡剂AC之外的其他原料混合均匀后进行密炼，调整密炼温度控制为86-91℃，保持4min后翻料；待密炼温度升至95℃，第二次翻料；待密炼温度升至101℃，第三次翻料，并加入交联剂BIBP和发泡剂AC，待密炼温度升至107℃，第四次翻料；待密炼温度升至112℃，第五次翻料，再密炼1min，最后倒料、开炼、造粒，得到环保发泡料米，经模压发泡制得环保发泡材料。
环保发泡材料可实现90天厌氧填埋后，降解85％(质量比)。降解实验参考GB/T 33797，填埋90天后，计算质量损失。
实施例3
一种EVA废弃料的处理方法，包括以下步骤：
步骤一，将废EVA鞋底、废EVA片材、废EVA边角料等废品投入破碎机中，破碎得到长度低于7cm，宽度小于5cm的块状破碎料；再将块状破碎料投入废料破碎机中，得到条状破碎料；
步骤二，将步骤一得到的条状破碎料、沙林树脂、PMP按重量比85:7:6的比例投入密炼机中，密炼温度逐渐上升，最高温度150℃，密炼时间21min，得块状密炼料；
步骤三，将密炼后的块状密炼料经螺杆挤出机、开炼机进行处理，以得到EVA回收膜；
其中，破碎机包括用于对EVA废弃料进行破碎的破碎组件，破碎组件包括相对设置的第一破碎辊及第二破碎辊，第一破碎辊与第二破碎辊之间形成对EVA废弃料破碎的破碎通道，第一破碎辊表面为光滑面，第二破碎辊表面开设有多个破碎凹槽；第一破碎辊与第二破碎辊的间隙小于3mm；具体的，破碎凹槽倾斜设置在第二破碎辊表面，倾斜角度为15°；进一步的，破碎凹槽沿径向呈上大下小的结构，破碎凹槽的间隙是8mm，凹槽的宽度1mm、深度0.3mm，凹槽成梯形，梯形短边是0.1mm。
EVA回收膜的厚度为0.008mm，PMP为脂肪酸类低聚物。
步骤三中，螺杆挤出机的基础温度为140℃；开炼机具体操作为：温度低于65℃压延成膜。
一种基于EVA废弃料的环保发泡材料，由以下重量份的原料组成；
Figure PCTCN2022114521-appb-000005
其制备方法包括以下步骤：先将除交联剂BIBP和发泡剂AC之外的其他原料混合均匀后进行密炼，调整密炼温度控制为86-91℃，保持4min后翻料；待密炼温度升至95℃，第二次翻料；待密炼温度升至101℃，第三次翻料，并加入交联剂BIBP和发泡剂AC，待密炼温度升至107℃，第四次翻料；待密炼温度升至112℃，第五次翻料，再密炼1min，最后倒料、开炼、造粒，得到环保发泡料米，经模压发泡制得环保发泡材料。
环保发泡材料可实现90天厌氧填埋后，降解94％(质量比)。降解实验参考GB/T 33797，填埋90天后，计算质量损失。
对比例1
其原料组成及制备方法与实施例3基本一致，区别在于：EVA回收膜 的制备只包括步骤一的破碎处理；且环保发泡材料的原料组成不包括SEBS。
将实施例1至实施例3及对比例进行相应测试，获得如下数据：
其中，压缩变形测试参考HG/T2876(温度50℃、时间6小时、压缩比例50％)，回弹率测试采用GT-7042-VAA垂直弹性试验机，苯乙酮含量和2-苯基-2-丙醇含量是鞋底室温敞开放置24小时后经丙酮萃取再利用GCMS测试分析(检出限2mg/kg))。
Figure PCTCN2022114521-appb-000006
通过上述表格可知，本申请制备的环保发泡材料压缩变形率小，回弹性高，符合鞋底的使用需要；且经过破碎、密炼、开炼处理得到的EVA回收膜中苯乙酮和2-苯基-2-丙醇含量均小于20mg/kg，符合REACH法规和“有害化学物质零排放”(ZDHC)的环保要求，符合国际品牌的环保要求。
以上所述，仅为本发明的较佳实施例而已，故不能以此限定本发明实施的范围，即依本发明申请专利范围及说明书内容所作的等效变化与 修饰，皆应仍属本发明专利涵盖的范围内。
工业实用性
本发明公开了一种基于EVA废弃料的环保发泡材料及EVA废弃料的处理方法，处理方法包括以下步骤：步骤一，将废EVA鞋底、废EVA片材、废EVA边角料等废弃料破碎得到条状破碎料；步骤二，将步骤一得到的条状破碎料、沙林树脂、PMP按重量比85:4-10:4-8的比例投入密炼机中，密炼温度逐渐上升，最高温度150℃，密炼时间18-25min，得块状密炼料；步骤三，将密炼后的块状密炼料经螺杆挤出机、开炼机进行处理，以得到EVA回收膜；本发明通过限定EVA废弃料的具体处理方式，实现对EVA鞋底料头、次品、废品和边角料的资源回收再利用，缓解白色污染带来的环境问题，经过处理后的EVA废弃料在鞋底制备中，添加比例可增加到70％以上，大大减少资源的浪费，提高废弃料的利用率,具有工业实用性。

Claims (10)

  1. 一种EVA废弃料的处理方法，其特征在于：包括以下步骤：
    步骤一，将废EVA鞋底、废EVA片材、废EVA边角料等废品破碎得到长度低于7cm，宽度小于5cm的块状破碎料；再将块状破碎料投入废料破碎机中，得到条状破碎料；
    步骤二，将步骤一得到的条状破碎料、沙林树脂、PMP按重量比85:4-10:4-8的比例投入密炼机中，密炼温度逐渐上升，最高温度150℃，密炼时间18-25min，得块状密炼料；
    步骤三，将密炼后的块状密炼料经螺杆挤出机、开炼机进行处理，以得到EVA回收膜；
    所述废料破碎机包括用于对EVA废弃料进行破碎的破碎组件，破碎组件包括相对设置的第一破碎辊及第二破碎辊，第一破碎辊与第二破碎辊之间形成对EVA废弃料破碎的破碎通道，第一破碎辊表面为光滑面，第二破碎辊表面开设有多个破碎凹槽，第一破碎辊与第二破碎辊之间的辊隙小于3mm。
  2. 根据权利要求1所述的一种EVA废弃料的处理方法，其特征在于：所述破碎凹槽倾斜设置在第二破碎辊表面，倾斜角度为10-45°。
  3. 根据权利要求1所述的一种EVA废弃料的处理方法，其特征在于：所述破碎凹槽沿径向呈上大下小的结构。
  4. 根据权利要求1所述的一种EVA废弃料的处理方法，其特征在于：所述PMP为脂肪酸类低聚物。
  5. 根据权利要求1所述的一种EVA废弃料的处理方法，其特征在于：所述步骤三中，螺杆挤出机的基础温度为130-150℃。
  6. 根据权利要求1所述的一种EVA废弃料的处理方法，其特征在于：所述步骤三中，开炼机具体操作为：温度低于65℃压延成膜。
  7. 根据权利要求6所述的一种EVA废弃料的处理方法，其特征在于：所述EVA回收膜的厚度小于或等于0.02mm。
  8. 一种基于EVA废弃料的环保发泡材料，其特征在于：由以下重量份的原料组成；
    Figure PCTCN2022114521-appb-100001
  9. 根据权利要求8所述的一种基于EVA废弃料的环保发泡材料，其特征在于：其制备方法包括以下步骤：先将除交联剂BIBP和发泡剂AC之外的其他原料混合均匀后进行密炼，调整密炼温度控制为86-91℃，保持4min后翻料；待密炼温度升至95℃，第二次翻料；待密炼温度升至 101℃，第三次翻料，并加入交联剂BIBP和发泡剂AC，待密炼温度升至107℃，第四次翻料；待密炼温度升至112℃，第五次翻料，再密炼1min，最后倒料、开炼、造粒，得到环保发泡料米，经模压发泡制得环保发泡材料。
  10. 根据权利要求1所述的一种基于EVA废弃料的环保发泡材料，其特征在于：所述生物降解剂是聚烯烃接枝改性产物。
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