WO2022011542A1 - 回收pet塑料瓶再制pet复合材料母粒及制法与发泡鞋材的应用 - Google Patents

回收pet塑料瓶再制pet复合材料母粒及制法与发泡鞋材的应用 Download PDF

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WO2022011542A1
WO2022011542A1 PCT/CN2020/101833 CN2020101833W WO2022011542A1 WO 2022011542 A1 WO2022011542 A1 WO 2022011542A1 CN 2020101833 W CN2020101833 W CN 2020101833W WO 2022011542 A1 WO2022011542 A1 WO 2022011542A1
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Prior art keywords
pet
vinyl acetate
polymer
ethylene
polyethylene terephthalate
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PCT/CN2020/101833
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English (en)
French (fr)
Inventor
许智仁
许佳鸣
黄羿儒
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驰绿国际股份有限公司
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Priority to PCT/CN2020/101833 priority Critical patent/WO2022011542A1/zh
Priority to EP20944966.9A priority patent/EP4183832A4/en
Priority to KR1020237001734A priority patent/KR20230025002A/ko
Priority to JP2022579059A priority patent/JP2023531685A/ja
Publication of WO2022011542A1 publication Critical patent/WO2022011542A1/zh

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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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • 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
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
    • 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
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/26—Scrap or recycled material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7158—Bottles
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches
    • 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 present invention relates to a kind of master batch material;
  • a kind of composite material master batch made of recycled polyethylene terephthalate (PET) and ethylene-vinyl acetate copolymer (EVA) and its preparation method and application.
  • PET polyethylene terephthalate
  • EVA ethylene-vinyl acetate copolymer
  • Poly-Alkylene Terephthalate is very good, especially polyethylene terephthalate (PET) is better; therefore, it is used in fibers, films, resins, etc.
  • PET polyethylene terephthalate
  • Related materials and food fields such as drinking water and carbonated beverage bottles are mass-produced and used.
  • material recycling along with mass production and use, a large number of wastes such as fibers, films, resin products and unqualified PET products are also produced, causing environmental problems that cannot be ignored. Therefore, material recycling (Material Recycle) Various methods have been proposed.
  • the object of the present invention is to provide a kind of reclaimed PET plastic bottle to remanufacture the composite material master batch of polyethylene terephthalate (PET) and ethylene-vinyl acetate copolymer (EVA) and preparation method thereof
  • PET polyethylene terephthalate
  • EVA ethylene-vinyl acetate copolymer
  • the recycled PET and EVA are combined with macromolecular coupling agent to be melted, kneaded and modified to form a new polymer alloy.
  • the purpose of recycling and reusing waste polyethylene terephthalate (PET) and reducing carbon and environmental protection also reduces the demand for fresh PET polymer materials, thereby reducing the demand for petrochemical raw materials.
  • the present invention provides a kind of recycled PET plastic bottle to make PET composite material master batch, which comprises: polyethylene terephthalate (PET), a polymer made after recycling waste packaging materials and textiles.
  • Ethylene terephthalate recycled material r-PET
  • EVA ethylene-vinyl acetate copolymer
  • macromolecular coupling agent wherein, based on the total weight of the composite material masterbatch as 100wt%, all
  • the content range of the polyethylene terephthalate is 25-65wt%
  • the content range of the ethylene-vinyl acetate copolymer is 30-70wt%
  • the content range of the macromolecular coupling agent is 2-10wt% .
  • the present invention also provides a method for reclaiming PET plastic bottles to make PET composite material masterbatch, the method steps comprising:
  • Material acquisition steps Provide ethylene-vinyl acetate copolymer (EVA), macromolecular coupling agent and recycled polyethylene terephthalate (r-PET) recycled from waste packaging materials or textiles. Based on the weight of 100wt%, the content of the polyethylene terephthalate recycled material ranges from 25 to 65wt%, the content of the ethylene-vinyl acetate copolymer ranges from 30 to 70wt%, and the macromolecular coupling The content of the agent is in the range of 2-10wt%;
  • Compound melting step using a loss-in-weight metering system, the ethylene-vinyl acetate copolymer (EVA), the macromolecular coupling agent and the polyethylene terephthalate (PET) are respectively mixed in proportions.
  • material to form a polymer glue using a twin-screw extruder at a temperature of 160-245 ° C and an average shear rate of 100-300/second (sec -1 ), the polymer glue is 100-250kg/
  • the extrusion amount of hr is extruded into strips, and at the same time, the screw is controlled to first heat up and then cool down within the aforementioned temperature range during the process of extruding the polymer glue;
  • the step of drawing strips of semi-finished products controlling the twin-screw extruder to extrude the polymer composite glue into strips, and guiding the strip-shaped polymer composite glue to cool through the water channel;
  • Cutting and granulating step controlling the twin-screw extruder to cut the cooled strip-shaped polymer glue into granules and then vibrating and sieving to obtain the composite material master batch.
  • Another object of the present invention is to provide an application method of the composite material masterbatch of the aforementioned recycled polyethylene terephthalate (PET) and ethylene-vinyl acetate copolymer (EVA) in the manufacture of shoe materials.
  • the composite material masterbatch is mixed with ethylene-vinyl acetate copolymer (EVA) and thermoplastic elastic material, and then the foam molding technology is used to manufacture the shoe material of a specific shape, so that the purpose of recycling and reusing waste PET can be achieved. Reduce the demand for fresh PET polymer materials in shoe manufacturing.
  • the present invention provides a method for reclaiming PET plastic bottles to reprocess PET composite material masterbatches for the manufacture of shoe materials.
  • the method steps include:
  • Material acquisition steps Provide ethylene-vinyl acetate copolymer (EVA), macromolecular coupling agent and recycled polyethylene terephthalate (r-PET) recycled from waste packaging materials and textiles. Based on the weight of 100wt%, the content of the polyethylene terephthalate recycled material ranges from 25 to 65wt%, the content of the ethylene-vinyl acetate copolymer ranges from 30 to 70wt%, and the macromolecular coupling The content of the agent is in the range of 2-10wt%;
  • Compound melting step using a loss-in-weight metering system, the ethylene-vinyl acetate copolymer (EVA), the macromolecular coupling agent and the polyethylene terephthalate (PET) are respectively mixed in proportions.
  • EVA ethylene-vinyl acetate copolymer
  • PET polyethylene terephthalate
  • the polymer glue is 100-250kg/
  • the extruded amount of hr is extruded into strips, and at the same time, the screw is controlled to be within the aforementioned temperature range during the process of extruding the polymer glue, starting from the feeding and starting from the feed to 160, 180, 190, 200, 220, 230, 240, 245 , 240, 235 °C temperature to the polymer glue to carry out segmental heating of first heating and then cooling;
  • the step of drawing strips of semi-finished products controlling the twin-screw extruder to extrude the polymer composite glue into strips, and guiding the strip-shaped polymer composite glue to cool through the water channel;
  • the step of cutting and granulating controlling the twin-screw extruder to cut the cooled strip-shaped polymer glue into granules and then vibrating and sieving to obtain the composite material masterbatch;
  • the step of fine-tuning the foaming mold according to the preset shoe material size, adjust the length, width and/or height of the cavity of the foaming mold, wherein the fine-tuning range of the length is 5-10mm, and the fine-tuning range of the width is 5-10mm, The fine-tuning range of thickness is 10-20mm;
  • Foaming molding step mixing the composite material master batch, ethylene-vinyl acetate copolymer (EVA), and elastic material into a mold, and preparing the shoe material through foam molding technology.
  • EVA ethylene-vinyl acetate copolymer
  • Figure 1 shows the appearance of a sheet foamed in a full-scale mold using recycled polyethylene terephthalate (r-PET).
  • FIG. 2 is the appearance of the T-shaped mold made from the composite material masterbatch containing the polyethylene terephthalate recycled material (r-PET) of the present invention.
  • Figure 3 shows the appearance of a sheet foamed in a full-scale mold using EVA material.
  • Figure 4 is a graph showing the appearance of a sheet foamed in a modified size mold using recycled polyethylene terephthalate (r-PET).
  • the composite material master batch of recycled PET and EVA of the present invention includes polyethylene terephthalate (PET), ethylene-vinyl acetate copolymer (EVA) and macromolecular coupling agent;
  • PET polyethylene terephthalate
  • EVA ethylene-vinyl acetate copolymer
  • macromolecular coupling agent The total weight of the pellets is 100 wt %, the content of the polyethylene terephthalate is in the range of 25-65 wt %, the content of the ethylene-vinyl acetate copolymer is in the range of 30-70 wt %, and the macromolecular
  • the content of the linking agent ranges from 2 to 10 wt%.
  • the polyethylene terephthalate is a recycled polyethylene terephthalate material (recycled PET, r-PET) made from waste packaging materials and textiles; the The intrinsic viscosity (IV) of polyethylene terephthalate recycled material is 0.6-1.0dL/g PET material.
  • the aforementioned waste packaging materials include containers made of PET, such as PET plastic bottles.
  • the vinyl acetate (VA) content of the ethylene-vinyl acetate copolymer (EVA) is 8-40 wt %
  • the melt flow rate (Melt mass- flow rate, MFR) is 1-10g per 10 minutes (1-10g/10min) at 190°C/2.16kg.
  • the macromolecular coupling agent may be a macromolecule or a grafted macromolecule without an epoxy functional group (Epoxy), or a macromolecule with an epoxy functional group (Epoxy).
  • the macromolecular coupling agent may also contain a primary amine (Primary (1°) amine) functional group, a secondary amine (Secondary (2°) amine) functional group or A grafted polymer (oligomer) of isocyanate (Isocyanate); wherein, the macromolecular coupling agent is preferably a grafted polymer or polymer with an epoxy functional group (Epoxy).
  • the macromolecular coupling agent can be selected from glycidyl methacrylate (GMA, Glycidyl methacrylate), maleic anhydride (maleic anhydride, MA, Maleic anhydride) or acrylic acid (AA, Acrlic acid);
  • the macromolecular coupling agent is preferably selected from glycidyl methacrylate (GMA), especially the grafting of glycidyl methacrylate (GMA) to ethylene-vinyl acetate copolymer (EVA) is high Molecules are most preferred.
  • the macromolecular coupling agent is a macromolecule or grafted macromolecule with an epoxy functional group (Epoxy)
  • the macromolecular coupling agent is preferably a macromolecular coupling agent containing 3-16 mol% epoxy functional group.
  • the composite material masterbatch of the present invention is prepared by melting and kneading the polyethylene terephthalate (PET), ethylene-vinyl acetate copolymer (EVA) and macromolecular coupling agent to form a polymer alloy ).
  • PET polyethylene terephthalate
  • EVA ethylene-vinyl acetate copolymer
  • macromolecular coupling agent to form a polymer alloy .
  • PET and EVA are subjected to etherification reaction or esterification reaction after adding a macromolecular coupling agent, so as to achieve the purpose of material modification, so that PET and EVA are well compatible to form the macromolecular glue.
  • PET is terminal organic acid functional group (carboxyl group):
  • the following structural formula 2 shows the structural formula of the polymer glue formed by the esterification reaction of PET and EVA after adding a macromolecular coupling agent, and PET is a terminal hydroxyl group:
  • the composite material masterbatch of the present invention uses polyethylene terephthalate (PET), ethylene-vinyl acetate copolymer (EVA) and epoxy functionalized EVA (Epoxy functionalized EVA) ) (that is, the macromolecular coupling agent) is represented by the following chemical formula 1, chemical formula 2, and chemical formula 3 in sequence.
  • PET polyethylene terephthalate
  • EVA ethylene-vinyl acetate copolymer
  • epoxy functionalized EVA epoxy functionalized EVA
  • n 100 moles in Chemical Formula 1.
  • reaction formula 1 shows the mechanism of the etherification reaction between PET and epoxy-functionalized EVA.
  • An etherification reaction compound having an EVA-philic end group and a PET-friendly end group is generated by Reaction Formula 1, whereby the following [Reaction Formula 2] shows the reaction mechanism of the etherification reaction compound being compatible with EVA and PET.
  • reaction formula 3 shows the mechanism of the esterification reaction between PET and epoxy-functional EVA.
  • reaction formula 3 An esterification reaction compound having an EVA-friendly end group and a PET-friendly end group is generated by reaction formula 3, and thus, the following reaction formula 4 shows the reaction mechanism that the esterification reaction compound is compatible with EVA and PET.
  • the present invention recycles the steps of the preparation method of the composite material master batch of PET and EVA comprising:
  • Compound melting step using a loss-in-weight metering system, the ethylene-vinyl acetate copolymer (EVA), the macromolecular coupling agent and the polyethylene terephthalate (PET) are respectively mixed in proportions.
  • material to form a polymer glue using a twin-screw extruder at a temperature of 160-245 ° C and an average shear rate of 100-300/second (sec -1 ), the polymer glue is 100-250kg/
  • the extrusion amount of hr is extruded into strips, and at the same time, the screw is controlled to first heat up and then cool down within the aforementioned temperature range during the process of extruding the polymer glue;
  • the step of drawing strips of semi-finished products controlling the twin-screw extruder to extrude the polymer composite glue into strips, and guiding the strip-shaped polymer composite glue to cool through the water channel;
  • Cutting and granulating step controlling the twin-screw extruder to cut the cooled strip-shaped polymer glue into granules and then vibrating and sieving to obtain the composite material master batch.
  • the screw in the step of melting the rubber compound, is in the process of extruding the polymer compound glue, starting from feeding the material, in sequence at 160, 180, 190, 200, 220, 230, 240, At temperatures of 245, 240, and 235° C., the polymer adhesive is heated in stages by first heating up and then cooling down.
  • EVA cracking 270 ° C
  • PET, EVA and epoxy-functionalized EVA are made to reach a preliminary reaction in the melting section to avoid EVA cracking and epoxy-functionalized EVA.
  • Oxygen ring-opening self-polymerization reaction results in the inability of r-PET and EVA to form a uniform polymer glue, which eventually destroys the foaming uniformity of the r-PET/EVA glue.
  • the method for reclaiming and reproducing the composite material master batch of PET and EVA of the present invention also includes the step of collecting and bagging after the step of cutting and granulating, which combines the sieved granular polymer with glue ( That is, the composite material masterbatch) is collected and bagged.
  • the composite material masterbatch prepared by the aforementioned ratio and preparation method of the present invention is mainly used in the field of shoe material manufacturing, but is not limited thereto.
  • the composite material masterbatch is used for mixing with ethylene-vinyl acetate copolymer (EVA) and thermoplastic elastic material to make shoe material through foam molding technology.
  • EVA ethylene-vinyl acetate copolymer
  • the composite material master batch of the present invention is used for the method for shoe material manufacture, and its method steps comprise:
  • Material acquisition steps Provide ethylene-vinyl acetate copolymer (EVA), macromolecular coupling agent and recycled polyethylene terephthalate (r-PET) recycled from waste packaging materials and textiles. Based on the weight of 100wt%, the content of the polyethylene terephthalate recycled material ranges from 25 to 65wt%, the content of the ethylene-vinyl acetate copolymer ranges from 30 to 70wt%, and the macromolecular coupling The content of the agent is in the range of 2-10wt%;
  • Compound melting step using a loss-in-weight metering system, the ethylene-vinyl acetate copolymer (EVA), the macromolecular coupling agent and the polyethylene terephthalate (PET) are respectively mixed in proportions.
  • EVA ethylene-vinyl acetate copolymer
  • PET polyethylene terephthalate
  • the polymer glue is 100-250kg/
  • the extruded amount of hr is extruded into strips, and at the same time, the screw is controlled to be within the aforementioned temperature range during the process of extruding the polymer glue, starting from the feeding and starting from the feed to 160, 180, 190, 200, 220, 230, 240, 245 , 240, 235 °C temperature to the polymer glue to carry out segmental heating of first heating and then cooling;
  • the step of drawing strips of semi-finished products controlling the twin-screw extruder to extrude the polymer composite glue into strips, and guiding the strip-shaped polymer composite glue to cool through the water channel;
  • the step of cutting and granulating controlling the twin-screw extruder to cut the cooled strip-shaped polymer glue into granules and then vibrating and sieving to obtain the composite material masterbatch;
  • the step of fine-tuning the foaming mold according to the preset shoe material size, adjust the length, width and/or height of the cavity of the foaming mold, wherein the fine-tuning range of the length is 5-10mm, and the fine-tuning range of the width is 5-10mm, The fine-tuning range of thickness is 10-20mm;
  • Foaming molding step mixing the composite material master batch, ethylene-vinyl acetate copolymer (EVA), and elastic material into a mold, and preparing the shoe material through foam molding technology.
  • EVA ethylene-vinyl acetate copolymer
  • the polyethylene terephthalate (PET) of the composite material master batch of the present invention can be obtained from waste PET plastic bottles. Wherein, when polyethylene terephthalate (PET) is obtained from discarded PET plastic bottles, it is made from the known PET plastic bottle recycling technology (PET bottle recycling) to make the polyethylene terephthalate recycled. Material (r-PET).
  • PET PET plastic bottle recycling
  • the processing method of waste PET plastic bottles includes: crushing, washing, separating and drying; wherein, the crushing step is to cut the material into small pieces, and then, a little original material residue left on the pieces is removed, For example, shredded paper labels and plastic covers, etc., after these residues are removed by suitable methods, they are washed, separated and dried, and finally pure PET chips or PET flakes are made to form the polyethylene terephthalate of the present invention.
  • Recycled material r-PET
  • the material ratio composition of the composite material masterbatch of the present invention is shown in Examples 1-4 of the following [Table 1].
  • Example 1 (Examples 1-4 are based on the total amount of composite material masterbatch as 100wt%, and the material content unit is based on wt%)
  • Table 2 shows that the length and width of the composite masterbatch containing recycled PET are close to the standard length and width when the cavity thickness is 8 mm, and the thickness is 15% higher than the standard expansion rate. From the analysis and comparison of different steps, when a new mold needs to be opened, if the thickness of the mold cavity is more than 6mm, the length should be reduced by 4% compared with the original material, and the width should be reduced by 3 to 4%. 10% to 20%. Product dimensions are calculated based on thickness.
  • the present invention finds out the difference between the composite master batch containing polyethylene terephthalate recycled material (r-PET) and the conventional EVA material through a series of tests.
  • the raw material formula is adjusted, and the width and thickness of the composite material master batch of the present invention that affects the foamed product are modified into the mold, and through the test of the test piece mold as shown in Figure 3 and Figure 4, it is proved that after the mold is revised, the composite material master batch of the present invention is modified.
  • the foamed shoe material product (Fig. 4) produced can be the same size as the foamed product (Fig. 3) produced from the existing EVA material.

Abstract

提供一种回收PET塑料瓶再制PET复合材料母粒及制法与发泡鞋材的应用。通过将回收再制PET与EVA搭配大分子偶联剂进行熔融混炼改质变性形成新的高分子合胶，再利用高扭力押出机制成所述复合材料母粒；所述复合材料母粒能够与乙烯-醋酸乙烯共聚物(EVA)、热塑性弹性材料混合，并利用发泡成型技术制造鞋材，达到将废弃聚对苯二甲酸乙二酯(PET)回收再利用以及减碳、环境保护的目的，同时也减少新鲜PET高分子材料之需求，进而降低对于石化原料的需求。

Description

回收PET塑料瓶再制PET复合材料母粒及制法与发泡鞋材的应用 技术领域
本发明关于一种母粒材料；特别关于一种使用回收再制聚对苯二甲酸乙二酯(PET)和乙烯-醋酸乙烯共聚物(EVA)制成的复合材料母粒及其制法与应用。
背景技术
由于聚对苯二甲酸烯基酯(Poly-Alkylene Terephthalate)的化学安定性非常优良，尤其聚对苯二甲酸乙二酯(polyethylene terephthalate，PET)更佳；因而在纤维、薄膜、树脂等与生活相关的资材以及饮料水、碳酸饮料用瓶等食品领域上被大量生产、使用。但是伴随着大量生产、大量使用的同时，也大量地产生了纤维、薄膜、树脂制品等的废弃物以及不合格的PET制品，造成不可忽视的环境问题，因此，物质再利用(Material Recycle)的种种方法纷纷被提出来。
值得注意的是，在废弃物中占有极大份量的PET瓶，将PET瓶洗净再充填使用的方法，因为回收费用、安全性、卫生性以及再使用次数的限制等的因素而放弃；而将PET瓶回收熔融再利用的方法中，PET瓶本体所含的颜色染料造成回收再使用时的限制，甚或因此造成回收熔融时的污染，降低了PET瓶回收再制成品的良率。
发明内容
为克服上述技术问题，本发明的目的在于提供一种回收PET塑料瓶再制聚对苯二甲酸乙二酯(PET)与乙烯-醋酸乙烯共聚物(EVA)的复合材料母粒及其制法与发泡鞋材的应用，通过将回收再制PET与EVA搭配大分子偶联剂进行熔融混炼改质变性形成新的高分子合胶(Polymer alloy)，再利用押出机制成母粒，达到将废弃聚对苯二甲酸乙二酯(PET)回收再利用以及减碳、环境保护的目的，同时也减少新鲜PET高分子材料的需求，进而降低对于石化原料的需求。
为达上述目的，本发明所提供一种回收PET塑料瓶再制PET复合材料母粒，其包括：聚对苯二甲酸乙二酯(PET)，自废弃包装材与纺织品回收后再制的聚对苯二甲酸乙二酯再生材料(r-PET)；乙烯-醋酸乙烯共聚物(EVA)；以及大分子偶联剂；其中，以所述复合材料母粒的总重为100wt％计，所述聚对苯二甲酸乙二酯的含量范围为25-65wt％，所述乙烯- 醋酸乙烯共聚物的含量范围为30-70wt％，所述大分子偶联剂的含量范围为2-10wt％。
本发明另提供一种回收PET塑料瓶再制PET复合材料母粒的制法，其方法步骤包括：
取材步骤：提供乙烯-醋酸乙烯共聚物(EVA)、大分子偶联剂以及自废弃包装材或纺织品回收后再制的聚对苯二甲酸乙二酯再生材料(r-PET)，以材料总重为100wt％计，所述聚对苯二甲酸乙二酯再生材料的含量范围为25-65wt％，所述乙烯-醋酸乙烯共聚物的含量范围为30-70wt％，所述大分子偶联剂的含量范围为2-10wt％；
胶料熔融步骤：利用失重式(loss-in-weight)计量系统，将乙烯-醋酸乙烯共聚物(EVA)、大分子偶联剂及聚对苯二甲酸乙二酯(PET)按比例分别下料形成高分子合胶，使用双螺杆押出机于温度为160-245℃以及平均剪切速率为100-300/秒(sec -1)条件下，将所述高分子合胶以100-250kg/hr的押出量押出成条状，同时控制螺杆于押出高分子合胶的过程中在前述温度范围内先升温再降温；
半成品抽条步骤：控制所述双螺杆押出机将压出成条状的所述高分子合胶抽条，并引导所述条状高分子合胶经过水道进行冷却；
切割造粒步骤：控制所述双螺杆押出机将冷却的条状高分子合胶切割成粒状后进行震动过筛，制得所述复合材料母粒。
本发明的另一目的在于提供前述回收再制聚对苯二甲酸乙二酯(PET)与乙烯-醋酸乙烯共聚物(EVA)的复合材料母粒于鞋材制造的应用方法，其将所述复合材料母粒与乙烯-醋酸乙烯共聚物(EVA)、热塑性弹性材料混合，再利用发泡成型技术制造特定造型的鞋材，由此，可确实达到将废弃PET回收再利用的目的，同时也减少鞋材制造对新鲜PET高分子材料的需求。
为达上述目的，本发明提供一种回收PET塑料瓶再制PET复合材料母粒于鞋材制造的应用方法，其方法步骤包括：
取材步骤：提供乙烯-醋酸乙烯共聚物(EVA)、大分子偶联剂以及自废弃包装材与纺织品回收后再制的聚对苯二甲酸乙二酯再生材料(r-PET)，以材料总重为100wt％计，所述聚对苯二甲酸乙二酯再生材料的含量范围为25-65wt％，所述乙烯-醋酸乙烯共聚物的含量范围为30-70wt％，所述大分子偶联剂的含量范围为2-10wt％；
胶料熔融步骤：利用失重式(loss-in-weight)计量系统，将乙烯-醋酸乙烯共聚物(EVA)、大分子偶联剂及聚对苯二甲酸乙二酯(PET)按比例分别下料形成高分子合胶，使用双螺杆押出机于温度为160-245℃以及平均剪切速率为100-300/秒(sec -1)条件下，将所述高分子合 胶以100-250kg/hr的押出量押出成条状，同时控制螺杆于押出高分子合胶的过程中在前述温度范围内，从入料开始以依序以160、180、190、200、220、230、240、245、240、235℃的温度对所述高分子合胶进行先升温再降温的分段加热；
半成品抽条步骤：控制所述双螺杆押出机将压出成条状的所述高分子合胶抽条，并引导所述条状高分子合胶经过水道进行冷却；
切割造粒步骤：控制所述双螺杆押出机将冷却的条状高分子合胶切割成粒状后进行震动过筛，制得所述复合材料母粒；
发泡模具微调步骤：根据预设鞋材尺寸，调整发泡模具的模穴的长度、宽度及/或高度尺寸，其中，长度的微调范围为5-10mm，宽度的微调范围为5-10mm，厚度的微调范围为10-20mm；
发泡成型步骤：将所述复合材料母粒及乙烯-醋酸乙烯共聚物(EVA)、弹性材料混合后入模，经发泡成型技术制得所述鞋材。
有关于本发明为达成上述目的，所采用的技术、手段及其他功效，兹举较佳可行实施例详细说明如后。
附图说明
图1为显示使用聚对苯二甲酸乙二酯再生材料(r-PET)于原尺寸模具中发泡制成的片材外观。
图2为以本发明含聚对苯二甲酸乙二酯再生材料(r-PET)的复合材料母粒制成的T型模外观。
图3为显示使用EVA材料于原尺寸模具中发泡制成的片材外观。
图4为显示使用聚对苯二甲酸乙二酯再生材料(r-PET)于修正尺寸模具中发泡制成的片材外观。
具体实施方式
下面将对本发明的技术方案进行清楚、完整的描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明特征与优点的一些实施例将在以下说明中详细叙述。应理解的是本发明能够在不 同的态样上具有各种的变化，然其皆不脱离本发明的范围，且其中的说明在本质上当作说明之用，而非用于限制本发明。
本发明的回收再制PET与EVA的复合材料母粒，包括聚对苯二甲酸乙二酯(PET)、乙烯-醋酸乙烯共聚物(EVA)及大分子偶联剂；以所述复合材料母粒的总重为100wt％计，所述聚对苯二甲酸乙二酯的含量范围为25-65wt％，所述乙烯-醋酸乙烯共聚物的含量范围为30-70wt％，所述大分子偶联剂的含量范围为2-10wt％。
于本发明实施例中，所述聚对苯二甲酸乙二酯系自废弃包装材与纺织品回收后再制的聚对苯二甲酸乙二酯再生材料(recycled PET，r-PET)；所述聚对苯二甲酸乙二酯再生材料的固有黏度(Intrinsic Viscosity，IV)为0.6-1.0dL/g的PET材料。前述废弃包装材包括PET制成的容器，例如PET塑料瓶。
于本发明实施例中，所述乙烯-醋酸乙烯共聚物(EVA)的醋酸乙烯酯(VA)的含量为8-40wt％，所述乙烯-醋酸乙烯共聚物的熔体流动速率(Melt mass-flow rate，MFR)在190℃/2.16kg的条件下为每10分钟1-10g(1-10g/10min)。
于本发明实施例中，所述大分子偶联剂可以是不具有环氧官能基团(Epoxy)的高分子或接枝高分子，也可以是具有环氧官能基团(Epoxy)的高分子或接枝高分子，又或者，所述大分子偶联剂还可以是含有一级胺(Primary(1°)amine)官能基团、二级胺(Secondary(2°)amine)官能基团或异氰酸酯(Isocyanate)的接枝高分子(寡聚物)；其中，所述大分子偶联剂以具有环氧官能基团(Epoxy)的接枝高分子或高分子为佳。具体地，所述大分子偶联剂可选自甲基丙烯酸缩水甘油酯(GMA，Glycidyl methacrylate)、马来酸酐(顺丁烯二酸酐，MA，Maleic anhydride)或丙烯酸(AA，Acrlic acid)；其中，所述大分子偶联剂以选择甲基丙烯酸缩水甘油酯(GMA)为佳，特别是甲基丙烯酸缩水甘油酯(GMA)接枝于乙烯-醋酸乙烯共聚物(EVA)的接枝高分子为最优选。进一步地，所述大分子偶联剂为具有环氧官能基团(Epoxy)的高分子或接枝高分子时，大分子偶联剂较佳为含有3-16mol％环氧官能基团的高分子衍生物。
本发明复合材料母粒系通过将所述聚对苯二甲酸乙二酯(PET)、乙烯-醋酸乙烯共聚物(EVA)及大分子偶联剂熔融混炼制成高分子合胶(Polymer alloy)。其中，PET与EVA系经由加入大分子偶联剂后进行醚化反应或酯化反应，达到材料改质，使PET与EVA良好地相容形成所述高分子合胶的目的。
如下结构式1，显示PET与EVA加入大分子偶联剂后进行醚化反应后形成的高分子合胶 结构式，PET为末端有机酸官能基团(carboxyl group)：
结构式1：
Figure PCTCN2020101833-appb-000001
如下结构式2，显示PET与EVA加入大分子偶联剂后进行酯化反应后形成的高分子合胶结构式，PET为末端羟基官能基团(hydroxyl group)：
结构式2：
HO-PET-大分子偶联剂-EVA本发明复合材料母粒使用的聚对苯二甲酸乙二酯(PET)、乙烯-醋酸乙烯共聚物(EVA)及环氧官能化EVA(Epoxy functionalized EVA)(即大分子偶联剂)的结构依序以下列化学式1、化学式2、化学式3表示。
化学式1：
Figure PCTCN2020101833-appb-000002
其中，化学式1的n＝100mole。
化学式2：
Figure PCTCN2020101833-appb-000003
其中，化学式2中，m+n＝100mol％时，m＝60-84mol％，n＝16-40mol％。
化学式3：
Figure PCTCN2020101833-appb-000004
其中，化学式3中，x+y+z＝100mol％时，x＝45-80mol％，y＝5-30mol％，z＝5-26mol％。
如下反应式1，显示PET与环氧官能化EVA进行醚化反应的机制。
反应式1：
Figure PCTCN2020101833-appb-000005
通过反应式1生成具有亲EVA端基及亲PET端基的醚化反应化合物，由此，如下[反应式2]，显示所述醚化反应化合物与EVA及PET兼容的反应机制。
反应式2：
Figure PCTCN2020101833-appb-000006
如下反应式3，显示PET与环氧官能化EVA进行酯化反应的机制。
反应式3：
Figure PCTCN2020101833-appb-000007
通过反应式3生成具有亲EVA端基及亲PET端基的酯化反应化合物，由此，如下反应式4，显示所述酯化反应化合物与EVA及PET兼容的反应机制。
反应式4：
Figure PCTCN2020101833-appb-000008
以上说明了本发明回收再制PET与EVA的复合材料母粒的配方及其材料熔融混炼相容的反应机制。以下说明本发明复合材料母粒的制法及其应用方法。
本发明回收再制PET与EVA的复合材料母粒的制法的步骤包括：
胶料熔融步骤：利用失重式(loss-in-weight)计量系统，将乙烯-醋酸乙烯共聚物(EVA)、大分子偶联剂及聚对苯二甲酸乙二酯(PET)按比例分别下料形成高分子合胶，使用双螺杆押出机于温度为160-245℃以及平均剪切速率为100-300/秒(sec -1)条件下，将所述高分子合胶以100-250kg/hr的押出量押出成条状，同时控制螺杆于押出高分子合胶的过程中在前述温度范围内先升温再降温；
半成品抽条步骤：控制所述双螺杆押出机将压出成条状的所述高分子合胶抽条，并引导所述条状高分子合胶经过水道进行冷却；
切割造粒步骤：控制所述双螺杆押出机将冷却的条状高分子合胶切割成粒状后进行震动过筛，制得所述复合材料母粒。
于本发明实施例，在所述熔融胶料步骤中，所述螺杆于押出高分子合胶的过程中，从入料开始以依序以160、180、190、200、220、230、240、245、240、235℃的温度对所述高分子合胶进行先升温再降温的分段加热。由此，通过后述温度加热段的控制，以保证EVA裂解之前(270℃)，在熔融段使PET、EVA及环氧官能化EVA达到初步反应，避免EVA裂解与环氧官能化EVA产生环氧开环自聚反应，导致r-PET与EVA无法形成均匀的高分子合胶，最终造成破坏r-PET/EVA合胶的发泡均匀性。
于本发明实施例中，本发明回收再制PET与EVA的复合材料母粒的制法中还包括在切割造粒步骤之后进行收集装袋步骤，其将过筛后的粒状高分子合胶(即所述复合材料母粒)收集装袋。
本发明经前述配比、制法制成的复合材料母粒主要应用于鞋材制造领域，但不限于此。于本发明实施例中，所述复合材料母粒用于和乙烯-醋酸乙烯共聚物(EVA)、热塑性弹性材料混合，以经由发泡成型技术制成鞋材。
本发明复合材料母粒用于鞋材制造的方法，其方法步骤包括：
取材步骤：提供乙烯-醋酸乙烯共聚物(EVA)、大分子偶联剂以及自废弃包装材与纺织品回收后再制的聚对苯二甲酸乙二酯再生材料(r-PET)，以材料总重为100wt％计，所述聚对苯二甲酸乙二酯再生材料的含量范围为25-65wt％，所述乙烯-醋酸乙烯共聚物的含量范围为30-70wt％，所述大分子偶联剂的含量范围为2-10wt％；
胶料熔融步骤：利用失重式(loss-in-weight)计量系统，将乙烯-醋酸乙烯共聚物(EVA)、大分子偶联剂及聚对苯二甲酸乙二酯(PET)按比例分别下料形成高分子合胶，使用双螺杆押出机于温度为160-245℃以及平均剪切速率为100-300/秒(sec -1)条件下，将所述高分子合胶以100-250kg/hr的押出量押出成条状，同时控制螺杆于押出高分子合胶的过程中在前述温度范围内，从入料开始以依序以160、180、190、200、220、230、240、245、240、235℃的温度对所述高分子合胶进行先升温再降温的分段加热；
半成品抽条步骤：控制所述双螺杆押出机将压出成条状的所述高分子合胶抽条，并引导所述条状高分子合胶经过水道进行冷却；
切割造粒步骤：控制所述双螺杆押出机将冷却的条状高分子合胶切割成粒状后进行震动过筛，制得所述复合材料母粒；
发泡模具微调步骤：根据预设鞋材尺寸，调整发泡模具的模穴的长度、宽度及/或高度尺寸，其中，长度的微调范围为5-10mm，宽度的微调范围为5-10mm，厚度的微调范围为10-20mm；
发泡成型步骤：将所述复合材料母粒及乙烯-醋酸乙烯共聚物(EVA)、弹性材料混合后入模，经发泡成型技术制得所述鞋材。
以下说明本发明含回收PET塑料瓶或渔网再制PET的复合材料母粒及其制法与发泡鞋材的应用的具体实施方式。
本发明复合材料母粒的聚对苯二甲酸乙二酯(PET)可取自废弃PET塑料瓶。其中，聚对苯二甲酸乙二酯(PET)取自废弃PET塑料瓶时，其系经由已知的PET塑料瓶回收技术(PET bottle recycling)制成所述聚对苯二甲酸乙二酯再生材料(r-PET)。具体地，废弃PET塑料瓶的处理方法包括：破碎、洗涤、分离和干燥；其中，破碎步骤系将材料切碎成小碎片，接着，将留在所述些碎片上的少许原始物质残留物，如碎纸标签和塑料盖等，将所述些残留物以适合的方法除去后，进行洗涤、分离和干燥，最终制成纯PET碎片或PET薄片，形成本发明聚对苯二甲酸乙二酯再生材料(r-PET)。
本发明复合材料母粒的材料配比组成如下[表1]的实施例1-4所示。
表1(实施例1-4以复合材料母粒总量为100wt％计，材料含量单位以wt％计)
Figure PCTCN2020101833-appb-000009
如下列表2、表3及图1至图4所示，本发明含回收再制PET的复合材料母粒用于制备发泡鞋材时，本发明含回收再制PET的复合材料母粒在发泡制程中的膨胀率较习知EVA材料的膨胀率更大。如图1所示，本发明复合材料母粒于原尺寸模具中发泡制成的片材外观，明显外形不规则且线条变形，由此，本发明经以图2所示的T型模反复测试不同结构的产品，并进行测试对比，确定本发明含回收再制PET的复合材料母粒在发泡制程中的膨胀率较习知EVA材料的膨胀率更大，是以，使用本发明含聚对苯二甲酸乙二酯再生材料(r-PET)的复合材料母粒制造发泡鞋材时，需调整模具的模穴尺寸，以提高发泡产品的外观良率。
表2
Figure PCTCN2020101833-appb-000010
表2显示含回收再制PET的复合材料母粒在模穴厚度为8mm时长度和宽度较接近标准的长度和宽度，厚度比标准膨胀率增加15％。从不同阶梯分析对比来看，需新开模具时，如模穴厚度6mm以上，长度需比原使用材料降低4％膨胀率，宽度也需调降3至4％，厚度建议比原使用材料降低10％至20％。产品尺寸以厚度为基准进行计算。
Figure PCTCN2020101833-appb-000011
如表3所示，本发明通过一系列测试，找出含聚对苯二甲酸乙二酯再生材料(r-PET)的复合材料母粒和习知EVA材料的差异性，经过T型模具和原料配方来调整，将本发明复合材料母粒影响发泡产品的宽度和厚度修进模具内，通过如图3、图4的试片模的测试，证明修订模具后，本发明复合材料母粒所生产的发泡鞋材产品(图4)可以和现有的EVA材料生产的发泡产品(图3)尺寸一样。
综上所述，上述各实施例仅为本发明的较佳实施例而已，并不用以限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，皆应包含在本发明的保护范围内。

Claims (10)

  1. 一种回收PET塑料瓶再制PET复合材料母粒，其特征在于，包括：
    聚对苯二甲酸乙二酯，为自废弃包装材或纺织品回收后再制的聚对苯二甲酸乙二酯再生材料；
    乙烯-醋酸乙烯共聚物；以及
    大分子偶联剂；
    其中，以所述复合材料母粒的总重为100wt％计，所述聚对苯二甲酸乙二酯的含量范围为25-65wt％，所述乙烯-醋酸乙烯共聚物的含量范围为30-70wt％，所述大分子偶联剂的含量范围为2-10wt％。
  2. 根据权利要求1所述的回收PET塑料瓶再制PET复合材料母粒，其特征在于，所述聚对苯二甲酸乙二酯再生材料的固有黏度为0.6-1.0dL/g。
  3. 根据权利要求1所述的回收PET塑料瓶再制PET复合材料母粒，其特征在于，所述乙烯-醋酸乙烯共聚物的醋酸乙烯酯的含量为8-40wt％，所述乙烯-醋酸乙烯共聚物的熔体流动速率在190℃/2.16kg的条件下为每10分钟1-10g。
  4. 根据权利要求1所述的回收PET塑料瓶再制PET复合材料母粒，其特征在于，所述大分子偶联剂选自甲基丙烯酸缩水甘油酯、顺丁烯二酸酐、丙烯酸、含有一级胺官能基团的接枝高分子、含有二级胺官能基团的接枝高分子或者含有异氰酸酯的接枝高分子。
  5. 一种回收PET塑料瓶再制PET复合材料母粒的制法，其特征在于，所述制法步骤包括：
    取材步骤：提供乙烯-醋酸乙烯共聚物、大分子偶联剂以及自废弃包装材或纺织品回收后再制的聚对苯二甲酸乙二酯再生材料，以材料总重为100wt％计，所述聚对苯二甲酸乙二酯再生材料的含量范围为25-65wt％，所述乙烯-醋酸乙烯共聚物的含量范围为30-70wt％，所述大分子偶联剂的含量范围为2-10wt％；
    胶料熔融步骤：利用失重式计量系统，将乙烯-醋酸乙烯共聚物、大分子偶联剂及聚对苯二甲酸乙二酯按比例分别下料形成高分子合胶，使用双螺杆押出机于温度为160-245℃以及平均剪切速率为100-300/秒条件下，将所述高分子合胶以100-250kg/hr的押出量押出成条状，同时控制螺杆于押出高分子合胶的过程中在前述温度范围内先升温再降温；
    半成品抽条步骤：控制所述双螺杆押出机将压出成条状的所述高分子合胶抽条，并引导所述条状高分子合胶经过水道进行冷却；
    切割造粒步骤：控制所述双螺杆押出机将冷却的条状高分子合胶切割成粒状后进行震动 过筛，制得所述复合材料母粒。
  6. 根据权利要求5所述的回收PET塑料瓶再制PET复合材料母粒的制法，其特征在于，其熔融胶料步骤中，所述螺杆于押出高分子合胶的过程中，从入料开始以依序以160、180、190、200、220、230、240、245、240、235℃的温度对所述高分子合胶进行先升温再降温的分段加热。
  7. 根据权利要求6所述的回收PET塑料瓶再制PET复合材料母粒的制法，其特征在于，
    所述聚对苯二甲酸乙二酯再生材料的固有黏度为0.6-1.0dL/g；
    所述乙烯-醋酸乙烯共聚物的醋酸乙烯酯的含量为8-40wt％，所述乙烯-醋酸乙烯共聚物的熔体流动速率在190℃/2.16kg的条件下为每10分钟1-10g。
  8. 根据权利要求6所述的回收PET塑料瓶再制PET复合材料母粒的制法，其特征在于，所述大分子偶联剂选自甲基丙烯酸缩水甘油酯、顺丁烯二酸酐、丙烯酸、含有一级胺官能基团的接枝高分子、含有二级胺官能基团的接枝高分子或者含有异氰酸酯的接枝高分子。
  9. 一种回收PET塑料瓶再制PET复合材料母粒于鞋材制造的应用方法，其特征在于，其方法步骤包括：
    取材步骤：提供乙烯-醋酸乙烯共聚物、大分子偶联剂以及自废弃包装材或纺织品回收后再制的聚对苯二甲酸乙二酯再生材料，以材料总重为100wt％计，所述聚对苯二甲酸乙二酯再生材料的含量范围为25-65wt％，所述乙烯-醋酸乙烯共聚物的含量范围为30-70wt％，所述大分子偶联剂的含量范围为2-10wt％；
    胶料熔融步骤：利用失重式计量系统，将乙烯-醋酸乙烯共聚物、大分子偶联剂及聚对苯二甲酸乙二酯按比例分别下料形成高分子合胶，使用双螺杆押出机于温度为160-245℃以及平均剪切速率为100-300/秒条件下，将所述高分子合胶以100-250kg/hr的押出量押出成条状，同时控制螺杆于押出高分子合胶的过程中在前述温度范围内，从入料开始以依序以160、180、190、200、220、230、240、245、240、235℃的温度对所述高分子合胶进行先升温再降温的分段加热；
    半成品抽条步骤：控制所述双螺杆押出机将压出成条状的所述高分子合胶抽条，并引导所述条状高分子合胶经过水道进行冷却；
    切割造粒步骤：控制所述双螺杆押出机将冷却的条状高分子合胶切割成粒状后进行震动过筛，制得所述复合材料母粒；
    发泡模具微调步骤：根据预设鞋材尺寸，调整发泡模具的模穴的长度、宽度及/或高度尺 寸，其中，长度的微调范围为5-10mm，宽度的微调范围为5-10mm，厚度的微调范围为10-20mm；
    发泡成型步骤：将所述复合材料母粒及乙烯-醋酸乙烯共聚物、弹性材料混合后入模，经发泡成型技术制得所述鞋材。
  10. 根据权利要求9所述的回收PET塑料瓶再制PET的复合材料母粒于鞋材制造的应用方法，其特征在于，
    所述聚对苯二甲酸乙二酯再生材料的固有黏度为0.6-1.0dL/g；
    所述乙烯-醋酸乙烯共聚物的醋酸乙烯酯的含量为8-40wt％，所述乙烯-醋酸乙烯共聚物的熔体流动速率在190℃/2.16kg的条件下为每10分钟1-10g；
    所述大分子偶联剂选自甲基丙烯酸缩水甘油酯、顺丁烯二酸酐、丙烯酸、含有一级胺官能基团的接枝高分子、含有二级胺官能基团的接枝高分子或者含有异氰酸酯的接枝高分子。
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JP2023531685A (ja) 2023-07-25
KR20230025002A (ko) 2023-02-21

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