TWI755759B - Composite masterbatch for manufacturing pet by recycling beverage cans and its preparation method and application of foaming shoe material - Google Patents

Abstract

A composite masterbatch for manufacturing PET by recycling beyerage cans and its preparation method and application of foaming shoe material, which mixing the recycled PET and EVA with compatible agent to melt and modify to form a new polymer adhesive, and forming the composite masterbatch by a high torsion mechanism, the composite masterbatch can be mixed with EVA and thermoplastic elastomer, and manufacturing the shoe material by using the foaming technology, so as to achieve the objects of recycling the waste PET, carbon reduction and environmental protection, and reducing the demand of fresh PET materials, thus reducing the demand of petrochemical raw material.

Description

Composite material masterbatch of recycled PET bottle and its production method and foamed shoe material application

The invention relates to a master batch material; in particular, to a composite material master batch made of recycled polyethylene terephthalate (PET) and ethylene-vinyl acetate copolymer (EVA) and its preparation method and application.

Because the chemical stability of Poly-Alkylene Terephthalate is very good, especially polyethylene terephthalate (PET) is better; therefore, it is used in fibers, films, resins, etc. and life Related materials and food fields such as drinking water and carbonated beverage bottles are mass-produced and used. However, 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.

It is worth noting that the method of washing and refilling PET bottles, which account for a large amount of waste, has been abandoned due to factors such as recycling costs, safety, hygiene, and restrictions on the number of reuses; In the method of recycling, melting and reusing PET bottles, the color dyes contained in the PET bottle body The material causes the limitation of recycling and reuse, or even causes pollution when recycling and melting, which reduces the yield of PET bottle recycling and remanufacturing products.

In order to overcome the above-mentioned technical problems, the object of the present invention is to provide a kind of composite material master batch of reclaimed PET bottle and remanufactured polyethylene terephthalate (PET) and ethylene-vinyl acetate copolymer (EVA) and its preparation method and foaming For the application of shoe materials, the recycled PET and EVA are mixed with compatibilizer for melt-kneading, modification and modification to form a new polymer alloy. For the purpose of recycling ethylene diformate (PET), carbon reduction and environmental protection, it also reduces the demand for fresh PET polymer materials, thereby reducing the demand for petrochemical raw materials.

The reason is that, in order to achieve the above purpose, the present invention provides a composite material masterbatch containing recycled PET, which includes: polyethylene terephthalate (PET), which is a polymer produced after recycling waste packaging materials and textiles. Ethylene terephthalate recycled material (r-PET); ethylene-vinyl acetate copolymer (EVA); and compatibilizer; wherein, based on the total weight of the composite masterbatch as 100wt%, the polyethylene The content of ethylene diformate 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 content of the compatibilizer is in the range of 2-10 wt %.

The present invention further provides a method for preparing a composite material masterbatch containing recycled PET, the method steps include: a material-obtaining step: providing ethylene-vinyl acetate copolymer (EVA), a compatibilizer, and a reclaimed product obtained from waste packaging materials or textiles. Polyethylene terephthalate recycled material (r-PET), based on the total weight of the material as 100wt%, the content of the polyethylene terephthalate recycled material is in the range of 25-65wt%, the ethylene-vinyl acetate The content of the copolymer is in the range of 30-70wt%, and the content of the compatibilizer is in the range of 2-10wt%; The rubber compound melting step: using a loss-in-weight metering system, the ethylene-vinyl acetate copolymer ( EVA), compatibilizer and polyethylene terephthalate (PET) are respectively cut in proportion 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 Under the condition of per second (sec ^-1 ), the polymer composite glue is extruded into strips at an extrusion rate of 100-250kg/hr, and at the same time, the screw is controlled to heat up within the aforementioned temperature range during the process of extruding the polymer composite glue. Cooling; semi-finished product drawing step: control the twin-screw extruder to extrude the polymer glue into strips, and guide the strip-shaped polymer glue to cool through the water channel; cutting and granulation step: control the double The screw extruder cuts the cooled strip polymer glue into granules and then vibrates and sieves 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 recycled polyethylene terephthalate (PET) and ethylene-vinyl acetate copolymer (EVA) in the manufacture of shoe materials, which is to use the composite material of the composite material. The 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. In this way, the purpose of recycling and reusing waste PET can be achieved, and the reduction of The demand for fresh PET polymer materials in shoe material manufacturing.

In order to achieve the above-mentioned purpose, the present invention provides a kind of application method of the composite material master batch containing recycled PET in the manufacture of shoe materials. Recycled polyethylene terephthalate material (r-PET) after recycling of waste packaging materials and textiles, based on the total weight of the material as 100% by weight, the content of the polyethylene terephthalate recycled material is within the range of 25% -65wt%, the content of the ethylene-vinyl acetate copolymer is in the range of 30-70wt%, and the content of the compatibilizer is in the range of 2-10wt%; rubber compound melting step: use a loss-in-weight metering system , the ethylene-vinyl acetate copolymer (EVA), the compatibilizer and the polyethylene terephthalate (PET) are respectively cut in proportion to form a polymer glue, using a twin-screw extruder at a temperature of 160-245 ℃ And under the condition that the average shear rate is 100-300/second (sec ^-1 ), the polymer composite glue is extruded into strips at the extrusion rate of 100-250kg/hr, and the process of extruding the polymer composite glue by the screw is controlled at the same time. In the above-mentioned temperature range, the polymer glue is heated up and then cooled at a temperature of 160, 180, 190, 200, 220, 230, 240, 245, 240, 235 °C in sequence from the start of feeding. Section heating; semi-finished product drawing step: control the twin-screw extruder to extrude the polymer glue into strips, and guide the strip-shaped polymer glue to cool through the water channel; cutting and granulation step: control the The twin-screw extruder cuts the cooled strip-shaped polymer glue into granules, and then vibrates and sieves to obtain the composite material masterbatch; the fine-tuning step of the foaming mold: adjust the mold of the foaming mold according to the preset shoe material size The length, width and/or height of the hole, wherein the fine-tuning range of the length is 5-10mm, the fine-tuning range of the width is 5-10mm, and the fine-tuning range of the thickness is 10-20mm; foam molding step: the composite material mother The granules, ethylene-vinyl acetate copolymer (EVA) and elastic material are mixed and then put into a mold, and the shoe material is prepared by foaming molding technology.

Regarding the techniques, means and other effects adopted by the present invention to achieve the above-mentioned objects, preferred feasible embodiments are described in detail as follows.

Figure 1 shows the appearance of a sheet foamed in a full-scale mold using recycled polyethylene terephthalate (r-PET); Figure 2 shows the appearance of a T-shaped mold made from the composite material masterbatch containing polyethylene terephthalate recycled material (r-PET) of the present invention; Figure 3 shows the use of EVA material to foam in the original size mold The appearance of the finished sheet; Figure 4 shows the appearance of the sheet formed by foaming in a modified-size mold using recycled polyethylene terephthalate (r-PET).

In order to facilitate the understanding of the present invention, the following description is made with reference to the embodiments.

Some embodiments of the features and advantages of the present invention are set forth in detail in the following description. It should be understood that the present invention is capable of various changes in various aspects without departing from the scope of the present invention, and the descriptions herein are for illustrative purposes rather than limiting the present invention.

The composite material masterbatch of recycled PET and EVA of the present invention includes polyethylene terephthalate (PET), ethylene-vinyl acetate copolymer (EVA) and a compatibilizer; the total of the composite material masterbatch Weight is 100wt%, the content range of this polyethylene terephthalate is 25-65wt%, the content range of this ethylene-vinyl acetate copolymer is 30-70wt%, the content range of this compatibilizer is 2- 10wt%.

In the embodiment of the present invention, the polyethylene terephthalate is a recycled polyethylene terephthalate material (recycled PET, r-PET) made from waste packaging materials and textiles; the polyethylene terephthalate is The ethylene diformate recycled material is a PET material with an intrinsic viscosity (IV) of 0.6-1.0 dL/g. The aforementioned waste packaging materials include containers made of PET, such as PET bottles.

In the embodiment of the present invention, the content of vinyl acetate (VA) of the ethylene-vinyl acetate copolymer (EVA) is 8-40 wt %, and the melt flow rate (Melt mass-flow rate) of the ethylene-vinyl acetate copolymer is 8-40 wt %. , MFR) is 1-10g (1-10g/10min) per 10 minutes under the condition of 190°C/2.16kg.

In the embodiment of the present invention, the compatibilizer may be a polymer or grafted polymer without an epoxy functional group (Epoxy), or a polymer or grafted polymer with an epoxy functional group (Epoxy). Polymer, or, alternatively, the compatibilizer can also be a graft containing a primary (1°) amine functional group, a secondary (2°) amine (2°) amine functional group or an isocyanate (Isocyanate) Polymer (oligomer); wherein, the compatibilizer is preferably a grafted polymer or polymer with epoxy functional groups (Epoxy). Specifically, the compatibilizer can be selected from glycidyl methacrylate (GMA, Glycidyl methacrylate), maleic anhydride (maleic anhydride, MA, Maleic anhydride) or acrylic acid (AA, Acrlic acid); wherein, the The compatibilizer is preferably selected from glycidyl methacrylate (GMA), especially the grafted polymer of glycidyl methacrylate (GMA) grafted on ethylene-vinyl acetate copolymer (EVA). Further, when the compatibilizer is a macromolecule or grafted macromolecule with an epoxy functional group (Epoxy), the compatibilizer is preferably a macromolecule derivative containing 3-16 mol% of an epoxy functional group.

The composite material master batch of the present invention is made into a polymer alloy by melting and kneading the polyethylene terephthalate (PET), ethylene-vinyl acetate copolymer (EVA) and compatibilizer. Among them, PET and EVA are subjected to etherification reaction or esterification reaction after adding a compatibilizer to achieve material modification, so that PET and EVA are well compatible to form the polymer glue.

The following [Structural Formula 1] shows the structural formula of the polymer glue formed after PET and EVA are added with a compatibilizer and undergo an etherification reaction, and PET is a 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 compatibilizer. PET is a terminal hydroxyl group: [Structural Formula 2] HO-PET -Compatibilizer-EVA The polyethylene terephthalate (PET), ethylene-vinyl acetate copolymer (EVA) and epoxy functionalized EVA (Epoxy functionalized EVA) used in the composite material masterbatch of the present invention (ie compatible The structure of the agent) is represented by the following [Chemical formula 1], [Chemical formula 2], [Chemical formula 3] in order.

Here, n=100 moles in [Chemical Formula 1].

Wherein, in [Chemical formula 2], when m+n=100mol%, m=60-84mol%, and n=16-40mol%.

[Chemical formula 3]

Wherein, in [Chemical formula 3], when x+y+z=100mol%, x=45-80mol%, y=5-30mol%, and z=5-26mol%.

The following [Equation 1] shows the mechanism of the etherification reaction between PET and epoxy-functional EVA.

Through [reaction formula 1], an etherification reaction compound with EVA-philic end groups and PET-friendly end groups is generated, whereby the following [reaction formula 2] shows the reaction mechanism of the etherification reaction compound being compatible with EVA and PET.

The following [Equation 3] shows the mechanism of the esterification reaction between PET and epoxy-functionalized EVA.

[Reaction 3]

Through [reaction formula 3], an esterification reaction compound with EVA-friendly end group and PET-friendly end group is generated, whereby the following [reaction formula 4] shows the reaction mechanism of the esterification reaction compound being compatible with EVA and PET.

The above has explained the formula of the composite material master batch of recycled PET and EVA of the present invention and the reaction mechanism of the melt-kneading compatibility of the materials. The preparation method of the composite material masterbatch of the present invention and its application method are described below.

The steps of the method for reclaiming and reproducing the composite material master batch of PET and EVA in the present invention include: a rubber material melting step: using a loss-in-weight metering system, ethylene-vinyl acetate copolymer (EVA), compatibilizer and polyethylene terephthalate (PET) in proportion 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/sec (sec ^-1 ) conditions, the polymer composite glue is extruded into strips with an extrusion amount of 100-250kg/hr, 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 composite glue; semi-finished product drawing step : control the twin-screw extruder to extrude the polymer glue into strips, and guide the strip-shaped polymer glue to cool through the water channel; cutting and granulation step: control the twin-screw extruder to cool the The strip-shaped polymer glue is cut into granules and then vibrated and sieved to obtain the composite material master batch.

In the embodiment of the present invention, in the step of melting the rubber compound, the screw is in the process of extruding the polymer compound glue, starting from feeding the material, and starting at 160, 180, 190, 200, 220, 230, 240, 245 , 240, 235 ℃ temperature of this polymer glue is first heated and then cooled in stages to heat. Thereby, through the control of the temperature heating section described later, to ensure that before EVA cracking (270 ° C), PET, EVA and epoxy-functionalized EVA are initially reacted in the melting section to avoid EVA cracking and epoxy-functionalized EVA to produce epoxy The 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.

In the embodiment of the present invention, the method for reclaiming and reproducing the composite material masterbatch of PET and EVA of the present invention also includes a step of collecting and bagging after the step of cutting and granulating, which is to sieve the granular polymer glue ( That is, the composite material masterbatch) is collected and bagged.

The composite material masterbatch prepared by the above-mentioned ratio and preparation method of the present invention is mainly used in the field of shoe material manufacturing, but is not limited thereto. In the embodiment of the present invention, 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.

The composite material master batch of the present invention is used for the method for manufacturing shoe materials, and the method steps include: material acquisition step: providing ethylene-vinyl acetate copolymer (EVA), a compatibilizer, and polyparaphenylene obtained after recycling waste packaging materials and textiles Recycled ethylene terephthalate material (r-PET), based on the total weight of the material as 100wt%, the content of the polyethylene terephthalate recycled material is 25-65wt%, the ethylene-vinyl acetate copolymer content The content range is 30-70wt%, and the content range of the compatibilizer is 2-10wt%; the rubber material melting step: using a loss-in-weight metering system, ethylene-vinyl acetate copolymer (EVA), The compatibilizer and polyethylene terephthalate (PET) are separately cut in proportion to form a polymer glue, and a twin-screw extruder is used at a temperature of 160-245 ° C and an average shear rate of 100-300/sec ( sec ^-1 ), extrude the polymer glue into strips at an extrusion rate of 100-250kg/hr, and control the screw to be within the aforementioned temperature range during the process of extruding the polymer glue. The polymer composite is heated firstly and then cooled down at temperatures of 160, 180, 190, 200, 220, 230, 240, 245, 240, and 235°C in sequence; semi-finished product drawing step: control the twin screw The extruder will extrude the polymer composite glue into strips, and guide the strip-shaped polymer composite glue to pass through the water channel for cooling; cutting and granulation step: control the twin-screw extruder to make the cooled strip polymer composite glue. After the glue is cut into granules, it is vibrated and sieved to obtain the composite material master batch; the fine-tuning step of 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, the fine-tuning range of the width is 5-10mm, and the fine-tuning range of the thickness is 10-20mm; The elastic material is mixed and then put into a mold, and the shoe material is prepared by foaming molding technology.

The following describes the specific embodiments of the composite material masterbatch containing recycled PET bottles or remanufactured PET from fishing nets, its production method, and the application of foamed shoe materials.

The polyethylene terephthalate (PET) of the composite material masterbatch of the present invention can be obtained from discarded PET bottles. Wherein, when polyethylene terephthalate (PET) is obtained from discarded PET bottles, it is made into the polyethylene terephthalate recycled material through the known PET bottle recycling technology. (r-PET). Specifically, the processing method of the waste bottle 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, such as Shredded paper labels and plastic covers, etc., after these residues are removed by suitable methods, washing, separating and drying are carried out, and finally pure PET chips or PET flakes are made to form the polyethylene terephthalate recycled material of the present invention. (r-PET).

The material ratio composition of the composite material masterbatch of the present invention is shown in Examples 1-4 of [Table 1] below.

As shown in the following [Table 2], [Table 3] and Figures 1 to 4, when the composite material masterbatch containing recycled PET of the present invention is used to prepare foamed shoe materials, the composite material masterbatch containing recycled PET of the present invention The expansion rate of the pellets in the foaming process is larger than that of the conventional EVA material. As shown in FIG. 1 , the appearance of the sheet formed by foaming the composite material masterbatch of the present invention in the original size mold is obviously irregular in shape and the lines are deformed, whereby the present invention is repeated with the T-shaped mold shown in FIG. 2 Test products of different structures, and carry out test comparison, it is confirmed that the expansion rate of the composite material masterbatch containing recycled PET in the foaming process is larger than that of the conventional EVA material. When the composite material masterbatch of ethylene terephthalate recycled material (r-PET) is used to manufacture foamed shoe materials, it is necessary to adjust the cavity size of the mold to improve the appearance yield of the foamed product.

[Table 2]

[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 8mm, 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, the width should be reduced by 3 to 4%, and the thickness should be reduced by 10% compared with the original material. % to 20%. Product dimensions are calculated based on thickness.

As shown in [Table 3], the present invention finds out the difference between the composite material masterbatch containing polyethylene terephthalate recycled material (r-PET) and the conventional EVA material through a series of tests. The mold and the raw material formula are adjusted, and the width and thickness of the composite material masterbatch of the present invention affecting the foamed product are modified into the mold. Through the test of the test piece mold as shown in Figure 3 and Figure 4, it is proved that after the modification of the mold, the composite material of the present invention The foamed shoe material product (Figure 4) produced by the master batch can be the same size as the foamed product produced by the conventional EVA material (Figure 3).

Claims (10)

A composite material masterbatch containing recycled PET, comprising: polyethylene terephthalate (PET), which is a recycled polyethylene terephthalate material (r-PET) after recycling waste packaging materials or textiles ); ethylene-vinyl acetate copolymer (EVA); and a compatibilizer; wherein, based on the total weight of the composite master batch as 100 wt %, the content of the polyethylene terephthalate ranges from 25 to 65 wt % , the content of the ethylene-vinyl acetate copolymer is in the range of 30-70wt%, and the content of the compatibilizer is in the range of 2-10wt%; the polyethylene terephthalate, the ethylene-vinyl acetate copolymer and the phase The solvent is melted and kneaded according to the proportion to make the polymer composite glue. During the extrusion process, the polymer composite glue is first heated up and then cooled down to be heated in stages to make the composite material master batch. The composite material master batch is used to mix with ethylene- The vinyl acetate copolymer (EVA) and the elastic material are mixed and foamed to form the shoe material. The composite material masterbatch containing recycled PET as described in item 1 of the patent application scope, wherein the intrinsic viscosity (IV) of the polyethylene terephthalate recycled material (r-PET) is 0.6- 1.0dL/g. The composite material masterbatch containing recycled PET as described in item 1 of the patent application scope, wherein the vinyl acetate (VA) content of the ethylene-vinyl acetate copolymer (EVA) is 8-40wt%, the ethylene-vinyl acetate copolymer (EVA) is The melt flow rate (MFR) of the vinyl acetate copolymer is 1-10 g per 10 minutes under the condition of 190° C./2.16 kg. The composite material masterbatch containing recycled PET as described in the first item of the patent application scope, wherein the compatibilizer is selected from glycidyl methacrylate (GMA), maleic anhydride (MA), acrylic acid ( AA), a graft polymer containing a primary amine functional group, a graft polymer containing a secondary amine functional group, or a graft polymer containing an isocyanate. A method for producing a composite material masterbatch containing recycled PET, wherein the steps of the method include: a step of obtaining materials: providing ethylene-vinyl acetate copolymer (EVA), a compatibilizer, and a polyvinyl chloride produced after recycling waste packaging materials or textiles Ethylene terephthalate recycled material (r-PET), based on the total weight of the material as 100wt%, the content range of the polyethylene terephthalate recycled material is 25-65wt%, the ethylene-vinyl acetate copolymer The content range of the compatibilizer is 30-70wt%, and the content range of the compatibilizer is 2-10wt%; the rubber material melting step: using a loss-in-weight metering system, ethylene-vinyl acetate copolymer (EVA) , compatibilizer and polyethylene terephthalate (PET) are respectively cut in proportion 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/sec Under the condition of (sec ^-1 ), the polymer glue is extruded into strips with an extrusion amount of 100-250kg/hr, and 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; Semi-finished product drawing step: control the twin-screw extruder to extrude the polymer composite glue into strips, and guide the strip-shaped polymer composite glue to cool through the water channel; cutting and pelletizing step: control the twin-screw extrusion The machine cuts the cooled strip polymer glue into granules and then vibrates and sieves to obtain the composite material master batch; the composite material master batch is used to mix with ethylene-vinyl acetate copolymer (EVA) and elastic material to produce Bubble molding into shoe material. As described in item 5 of the scope of the patent application, in the method for producing composite material masterbatch containing recycled PET, in the step of melting the rubber compound, the screw is in the process of extruding the polymer compound glue, starting from feeding the material and starting with The temperature of 160, 180, 190, 200, 220, 230, 240, 245, 240, 235 ℃ is used to heat the polymer adhesive in stages by first heating up and then cooling down. The method for preparing composite material masterbatch containing recycled PET as described in item 6 of the scope of application for patent, wherein: the intrinsic viscosity (IV) of the polyethylene terephthalate regenerated material (r-PET) is 0.6-1.0dL/g; the vinyl acetate (VA) content of the ethylene-vinyl acetate copolymer (EVA) is 8-40wt%, and the melt flow rate (Melt mass-flow rate) of the ethylene-vinyl acetate copolymer (EVA) is 8-40wt%. , MFR) is 1-10 g per 10 minutes under the condition of 190 ° C/2.16 kg. The method for preparing composite material masterbatch containing recycled PET as described in item 6 of the scope of the application, wherein the compatibilizer is selected from glycidyl methacrylate (GMA), maleic anhydride (MA), Acrylic acid (AA), graft polymer containing primary amine functional group, graft polymer containing secondary amine functional group or graft polymer containing isocyanate. An application method of composite material masterbatch containing recycled PET in shoe material manufacturing, the method steps include: material acquisition step: providing ethylene-vinyl acetate copolymer (EVA), a compatibilizer, and recycling waste packaging materials or textiles. The polyethylene terephthalate recycled material (r-PET), based on the total weight of the material as 100wt%, the content of the polyethylene terephthalate recycled material ranges from 25 to 65wt%, the ethylene-acetic acid The content of the ethylene copolymer is in the range of 30-70 wt%, and the content of the compatibilizer is in the range of 2-10 wt%; the rubber compound melting step: using a loss-in-weight metering system, the ethylene-vinyl acetate copolymer is (EVA), compatibilizer and polyethylene terephthalate (PET) were respectively cut in proportion to form a polymer glue, using a twin-screw extruder at a temperature of 160-245°C and an average shear rate of 100- Under the condition of 300/second (sec ^-1 ), the polymer composite glue is extruded into strips at an extrusion rate of 100-250kg/hr, and at the same time, the screw is controlled to be within the aforementioned temperature range during the process of extruding the polymer composite glue. At the beginning of feeding, the polymer glue is heated in stages at a temperature of 160, 180, 190, 200, 220, 230, 240, 245, 240, and 235°C in sequence; Control the twin-screw extruder to extrude the polymer glue into strips, and guide the strip-shaped polymer glue to cool through the water channel; cutting and granulation step: control the twin-screw extruder to cool the strips The high-molecular polymer glue is cut into granules and then vibrated and sieved to obtain the composite material master batch; the fine-tuning step of the foaming mold: according to the preset shoe material size, adjust the length, width and/or length of the cavity of the foaming mold Height dimension, wherein, the fine-tuning range of length is 5-10mm, the fine-tuning range of width is 5-10mm, and the fine-tuning range of thickness is 10-20mm; foam molding step: the composite material master batch and ethylene-vinyl acetate copolymer (EVA) and the elastic material are mixed and then put into the mold, and the shoe material is obtained by the foaming molding technology. The application method of the composite material masterbatch containing recycled PET in the manufacture of shoe materials as described in item 9 of the patent application scope, wherein: the intrinsic viscosity of the polyethylene terephthalate recycled material (r-PET) (Intrinsic Viscosity, IV) is 0.6-1.0 dL/g; the vinyl acetate (VA) content of the ethylene-vinyl acetate copolymer (EVA) is 8-40 wt%, and the melt flow rate ( Melt mass-flow rate, MFR) is 1-10g per 10 minutes under the condition of 190℃/2.16kg; the compatibilizer is selected from glycidyl methacrylate (GMA), maleic anhydride (MA) , acrylic acid (AA), grafted polymer containing primary amine functional group, grafted polymer containing secondary amine functional group or grafted polymer containing isocyanate.

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