TW202200334A - Composite masterbatch for manufacturing pet by recycling beverage cans and its preparation method and application of foaming shoe material - Google Patents

Composite masterbatch for manufacturing pet by recycling beverage cans and its preparation method and application of foaming shoe material Download PDF

Info

Publication number
TW202200334A
TW202200334A TW109120420A TW109120420A TW202200334A TW 202200334 A TW202200334 A TW 202200334A TW 109120420 A TW109120420 A TW 109120420A TW 109120420 A TW109120420 A TW 109120420A TW 202200334 A TW202200334 A TW 202200334A
Authority
TW
Taiwan
Prior art keywords
pet
ethylene
vinyl acetate
eva
polymer
Prior art date
Application number
TW109120420A
Other languages
Chinese (zh)
Other versions
TWI755759B (en
Inventor
許智仁
許佳鳴
黃羿儒
Original Assignee
馳綠國際股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 馳綠國際股份有限公司 filed Critical 馳綠國際股份有限公司
Priority to TW109120420A priority Critical patent/TWI755759B/en
Publication of TW202200334A publication Critical patent/TW202200334A/en
Application granted granted Critical
Publication of TWI755759B publication Critical patent/TWI755759B/en

Links

Images

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/62Plastics recycling; Rubber recycling

Landscapes

  • Processes Of Treating Macromolecular Substances (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

A composite masterbatch for manufacturing PET by recycling beverage 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

回收寶特瓶再製PET之複合材料母粒及其製法與發泡鞋材之應用Composite masterbatch of recycled PET bottles and its production method and application of foamed shoe materials

本發明係關於一種母粒材料;特別關於一種使用回收再製聚對苯二甲酸乙二酯(PET)和乙烯-醋酸乙烯共聚物(EVA)製成的複合材料母粒及其製法與應用。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.

由於聚對苯二甲酸烯基酯(Poly-Alkylene Terephthalate)之化學安定性非常優良,尤其聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)更佳;因而在纖維、薄膜、樹脂等與生活相關的資材以及飲料水、碳酸飲料用瓶等食品領域上被大量生產、使用。但是伴隨著大量生產、大量使用的同時,也大量地產生了纖維、薄膜、樹脂製品等的廢棄物以及不合格的PET製品,造成不可忽視的環境問題,因此,物質再利用(Material Recycle)之種種方法紛紛被提出來。Because the chemical stability of Poly-Alkylene Terephthalate is very good, especially polyethylene terephthalate (PET) is better; 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.

值得注意的是,在廢棄物中佔有極大份量的PET瓶,將PET瓶洗淨再充填使用的方法,因為回收費用、安全性、衛生性以及再使用次數的限制等之因素而放棄;而將PET瓶回收熔融再利用的方法中,PET瓶本體所含的顏色染料造成回收再使用時的限制,甚或因此造成回收熔融時的污染,降低了PET瓶回收再製成品的良率。It is worth noting that the method of washing and refilling PET bottles, which account for a large amount of waste in the waste, was 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 body of the PET bottle limit the recycling and reuse, or even cause pollution during recycling and melting, which reduces the yield of recycled PET bottles.

為克服上述技術問題,本發明之目的在於提供一種回收寶特瓶再製聚對苯二甲酸乙二酯(PET)與乙烯-醋酸乙烯共聚物(EVA)之複合材料母粒及其製法與發泡鞋材之應用,透過將回收再製PET與EVA搭配相容劑進行熔融混煉改質變性形成新的高分子合膠(Polymer alloy),再利用押出機製成母粒,達到將廢棄聚對苯二甲酸乙二酯(PET)回收再利用以及減碳、環境保護之目的,同時也減少新鮮PET高分子材料之需求,進而降低對於石化原料的需求。In order to overcome the above-mentioned technical problems, the object of the present invention is to provide a composite material masterbatch of recycled PET bottles 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 a compatibilizer for melting, kneading, modification and modification to form a new polymer alloy, and then the extruder is used to form the masterbatch, so as to achieve the waste of polyparaphenylene. 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.

緣是,為達上述目的,本發明所提供一種含回收再製PET之複合材料母粒,其包括:聚對苯二甲酸乙二酯(PET),係自廢棄包裝材與紡織品回收後再製之聚對苯二甲酸乙二酯再生材料(r-PET);乙烯-醋酸乙烯共聚物(EVA);以及相容劑;其中,以該複合材料母粒之總重為100wt%計,該聚對苯二甲酸乙二酯的含量範圍為25-65wt%,該乙烯-醋酸乙烯共聚物的含量範圍為30-70wt%,該相容劑的含量範圍為2-10wt%。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 %.

本發明另提供一種含回收再製PET之複合材料母粒之製法,其方法步驟包括:The present invention also provides a method for preparing a composite material masterbatch containing recycled PET, the method steps comprising:

取材步驟:提供乙烯-醋酸乙烯共聚物(EVA)、相容劑以及自廢棄包裝材或紡織品回收後再製之聚對苯二甲酸乙二酯再生材料(r-PET),以材料總重為100wt%計,該聚對苯二甲酸乙二酯再生材料的含量範圍為25-65wt%,該乙烯-醋酸乙烯共聚物的含量範圍為30-70wt%,該相容劑的含量範圍為2-10wt%;Material acquisition steps: Provide ethylene-vinyl acetate copolymer (EVA), compatibilizer, and recycled polyethylene terephthalate (r-PET) recycled from waste packaging materials or textiles. The total weight of the material is 100wt %, the content range of the polyethylene terephthalate regenerated material is 25-65wt%, the content range of the ethylene-vinyl acetate copolymer is 30-70wt%, and the content range of the compatibilizer is 2-10wt% %;

膠料熔融步驟:利用失重式(loss-in-weight )計量系統,將乙烯-醋酸乙烯共聚物(EVA)、相容劑及聚對苯二甲酸乙二酯(PET)按比例分別下料形成高分子合膠,使用雙螺桿押出機於溫度為160-245℃以及平均剪切速率為100-300/秒(sec-1 )條件下,將該高分子合膠以100-250kg/hr之押出量押出成條狀,同時控制螺桿於押出高分子合膠的過程中在前述溫度範圍內先升溫再降溫;Melting step of rubber compound: Using a loss-in-weight metering system, ethylene-vinyl acetate copolymer (EVA), compatibilizer and polyethylene terephthalate (PET) are separately formed in proportions. The polymer composite glue is extruded at a rate of 100-250kg/hr using a twin-screw extruder at a temperature of 160-245°C and an average shear rate of 100-300/second (sec -1 ). It 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 adhesive;

半成品抽條步驟:控制該雙螺桿押出機將壓出成條狀之該高分子合膠抽條,並引導該條狀高分子合膠經過水道進行冷卻;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;

切割造粒步驟:控制該雙螺桿押出機將冷卻的條狀高分子合膠切割成粒狀後進行震動過篩,製得該複合材料母粒。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.

本發明之另一目的在於提供前述回收再製聚對苯二甲酸乙二酯(PET)與乙烯-醋酸乙烯共聚物(EVA)之複合材料母粒於鞋材製造之應用方法,其係將該複合材料母粒與乙烯-醋酸乙烯共聚物(EVA)、熱塑性彈性材料混合,再利用發泡成型技術製造特定造型之鞋材,藉此,可確實達到將廢棄PET回收再利用之目的,同時也減少鞋材製造對新鮮PET高分子材料之需求。Another object of the present invention is to provide an application method of the above-mentioned recycled polyethylene terephthalate (PET) and ethylene-vinyl acetate copolymer (EVA) composite material masterbatch 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 Demand for fresh PET polymer materials in shoe material manufacturing.

為達上述目的,本發明提供一種含回收再製PET之複合材料母粒於鞋材製造之應用方法,其方法步驟包括: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, and the method steps include:

取材步驟:提供乙烯-醋酸乙烯共聚物(EVA)、相容劑以及自廢棄包裝材與紡織品回收後再製之聚對苯二甲酸乙二酯再生材料(r-PET),以材料總重為100wt%計,該聚對苯二甲酸乙二酯再生材料的含量範圍為25-65wt%,該乙烯-醋酸乙烯共聚物的含量範圍為30-70wt%,該相容劑的含量範圍為2-10wt%;Material acquisition steps: Provide ethylene-vinyl acetate copolymer (EVA), compatibilizer, and recycled polyethylene terephthalate (r-PET) recycled from waste packaging materials and textiles. The total weight of the material is 100wt %, the content range of the polyethylene terephthalate regenerated material is 25-65wt%, the content range of the ethylene-vinyl acetate copolymer is 30-70wt%, and the content range of the compatibilizer is 2-10wt% %;

膠料熔融步驟:利用失重式(loss-in-weight )計量系統,將乙烯-醋酸乙烯共聚物(EVA)、相容劑及聚對苯二甲酸乙二酯(PET)按比例分別下料形成高分子合膠,使用雙螺桿押出機於溫度為160-245℃以及平均剪切速率為100-300/秒(sec-1 )條件下,將該高分子合膠以100-250kg/hr之押出量押出成條狀,同時控制螺桿於押出高分子合膠的過程中在前述溫度範圍內,從入料開始以依序以160、180、190、200、220、230、240、245、240、235℃之溫度對該高分子合膠進行先升溫再降溫之分段加熱;Melting step of rubber compound: Using a loss-in-weight metering system, ethylene-vinyl acetate copolymer (EVA), compatibilizer and polyethylene terephthalate (PET) are separately formed in proportions. The polymer composite glue is extruded at a rate of 100-250kg/hr using a twin-screw extruder at a temperature of 160-245°C and an average shear rate of 100-300/second (sec -1 ). It is extruded into strips, and at the same time, the screw is controlled within the aforementioned temperature range during the process of extruding the polymer compound glue. At a temperature of 235°C, the polymer glue is heated in stages by first heating up and then cooling down;

半成品抽條步驟:控制該雙螺桿押出機將壓出成條狀之該高分子合膠抽條,並引導該條狀高分子合膠經過水道進行冷卻;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;

切割造粒步驟:控制該雙螺桿押出機將冷卻的條狀高分子合膠切割成粒狀後進行震動過篩,製得該複合材料母粒;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;

發泡模具微調步驟:根據預設鞋材尺寸,調整發泡模具之模穴的長度、寬度及/或高度尺寸,其中,長度的微調範圍為5-10mm,寬度的微調範圍為5-10mm,厚度的微調範圍為10-20mm;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, and the fine-tuning range of the width is 5-10mm, The fine-tuning range of thickness is 10-20mm;

發泡成型步驟:將該複合材料母粒及乙烯-醋酸乙烯共聚物(EVA)、彈性材料混合後入模,經發泡成型技術製得該鞋材。Foaming molding step: the composite master batch, 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.

有關於本發明為達成上述目的,所採用之技術、手段及其他功效,茲舉較佳可行實施例詳細說明如後。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.

為利於對本發明的瞭解,以下結合實施例進行說明。In order to facilitate the understanding of the present invention, the following description is given in conjunction with the embodiments.

本發明特徵與優點的一些實施例將在以下說明中詳細敘述。應理解的是本發明能夠在不同的態樣上具有各種的變化,然其皆不脫離本發明的範圍,且其中的說明在本質上係當作說明之用,而非用於限制本發明。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.

本發明之回收再製PET與EVA之複合材料母粒,係包括聚對苯二甲酸乙二酯(PET)、乙烯-醋酸乙烯共聚物(EVA)及相容劑;以該複合材料母粒之總重為100wt%計,該聚對苯二甲酸乙二酯的含量範圍為25-65wt%,該乙烯-醋酸乙烯共聚物的含量範圍為30-70wt%,該相容劑的含量範圍為2-10wt%。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%.

於本發明實施例中,該聚對苯二甲酸乙二酯係自廢棄包裝材與紡織品回收後再製之聚對苯二甲酸乙二酯再生材料(recycled PET,r-PET);該聚對苯二甲酸乙二酯再生材料係固有黏度(Intrinsic Viscosity,IV)為0.6-1.0 dL/g之PET材料。前述廢棄包裝材包括PET製成之容器,例如寶特瓶。In the embodiment of the present invention, the polyethylene terephthalate is a recycled polyethylene terephthalate (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.

於本發明實施例中,該乙烯-醋酸乙烯共聚物(EVA)係醋酸乙烯酯(VA)的含量為8-40wt%,該乙烯-醋酸乙烯共聚物之熔體流動速率(Melt mass-flow rate,MFR)在190℃/2.16kg之條件下為每10分鐘1-10 g(1-10 g / 10 min)。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) at 190°C/2.16kg at 1-10 g per 10 minutes (1-10 g/10 min).

於本發明實施例中,該相容劑可以是不具有環氧官能基團(Epoxy)的高分子或接枝高分子,也可以是具有環氧官能基團(Epoxy)的高分子或接枝高分子,又或者,該相容劑還可以是含有一級胺(Primary(1°) amine)官能基團、二級胺(Secondary(2°) amine)官能基團或異氰酸酯(Isocyanate)的接枝高分子(寡聚物);其中,該相容劑以具有環氧官能基團(Epoxy)的接枝高分子或高分子為佳。具體地,該相容劑可選自甲基丙烯酸縮水甘油酯(GMA,Glycidyl methacrylate)、馬來酸酐(順丁烯二酸酐,MA,Maleic anhydride)或丙烯酸(AA,Acrlic acid);其中,該相容劑以選擇甲基丙烯酸縮水甘油酯(GMA)為佳,特別是甲基丙烯酸縮水甘油酯(GMA)接枝於乙烯-醋酸乙烯共聚物(EVA)的接枝高分子為最優選。進一步地,該相容劑為具有環氧官能基團(Epoxy)的高分子或接枝高分子時,相容劑較佳為含有3-16 mol%環氧官能基團的高分子衍生物。In the embodiment of the present invention, the compatibilizer may be a polymer or a grafted polymer without an epoxy functional group (Epoxy), or a polymer or a grafted polymer with an epoxy functional group (Epoxy). Polymer, or alternatively, the compatibilizer can also be a graft containing a functional group of primary amine (1°) amine, functional group of secondary amine (2°) or isocyanate (Isocyanate). Macromolecule (oligomer); wherein, the compatibilizer is preferably a grafted macromolecule or macromolecule with an epoxy functional group (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 graft polymer of glycidyl methacrylate (GMA) grafted on ethylene-vinyl acetate copolymer (EVA). Further, when the compatibilizer is a macromolecule or grafted macromolecule with epoxy functional groups (Epoxy), the compatibilizer is preferably a macromolecule derivative containing 3-16 mol% of epoxy functional groups.

本發明複合材料母粒係透過將該聚對苯二甲酸乙二酯(PET)、乙烯-醋酸乙烯共聚物(EVA)及相容劑熔融混煉製成高分子合膠(Polymer alloy)。其中,PET與EVA係經由加入相容劑後進行醚化反應或酯化反應,達到材料改質,使PET與EVA良好地相容形成該高分子合膠之目的。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.

如下[結構式1],顯示PET與EVA加入相容劑後進行醚化反應後形成的高分子合膠結構式,PET為末端有機酸官能基團(carboxyl group):The following [Structural Formula 1] shows the structural formula of the polymer glue formed by the etherification reaction of PET and EVA after adding a compatibilizer. PET is a terminal organic acid functional group (carboxyl group):

[結構式1]

Figure 02_image001
[Structural formula 1]
Figure 02_image001

如下[結構式2],顯示PET與EVA加入相容劑後進行酯化反應後形成的高分子合膠結構式,PET為末端羥基官能基團(hydroxyl 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:

[結構式2][Structural formula 2]

Figure 02_image002
本發明複合材料母粒使用的聚對苯二甲酸乙二酯(PET)、乙烯-醋酸乙烯共聚物(EVA)及環氧官能化EVA(Epoxy functionalized EVA)(即相容劑)之結構依序以下列[化學式1]、[化學式2]、[化學式3]表示。
Figure 02_image002
The structures of polyethylene terephthalate (PET), ethylene-vinyl acetate copolymer (EVA) and epoxy functionalized EVA (ie compatibilizer) used in the composite material masterbatch of the present invention are in order It is represented by the following [Chemical formula 1], [Chemical formula 2], and [Chemical formula 3].

[化學式1]

Figure 02_image003
[Chemical formula 1]
Figure 02_image003

其中,[化學式1]的 n=100 mole。Wherein, n=100 mole of [Chemical formula 1].

[化學式2]

Figure 02_image005
[Chemical formula 2]
Figure 02_image005

其中,[化學式2]中,m+n=100 mol%時, m=60-84mol%,n=16-40mol%。Wherein, in [Chemical formula 2], when m+n=100 mol%, m=60-84mol%, and n=16-40mol%.

[化學式3]

Figure 02_image006
[Chemical formula 3]
Figure 02_image006

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

如下[反應式1],顯示PET與環氧官能化EVA進行醚化反應之機制。The following [Equation 1] shows the mechanism of the etherification reaction between PET and epoxy-functional EVA.

[反應式1]

Figure 02_image007
[Reaction 1]
Figure 02_image007

透過[反應式1]生成具有親EVA端基及親PET端基之醚化反應化合物,藉此,如下[反應式2],顯示該醚化反應化合物與EVA及PET相容之反應機制。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.

[反應式2]

Figure 02_image009
[Reaction 2]
Figure 02_image009

如下[反應式3],顯示PET與環氧官能化EVA進行酯化反應之機制。The following [Equation 3] shows the mechanism of the esterification reaction between PET and epoxy-functionalized EVA.

[反應式3]

Figure 02_image011
[Reaction 3]
Figure 02_image011

透過[反應式3]生成具有親EVA端基及親PET端基之酯化反應化合物,藉此,如下[反應式4],顯示該酯化反應化合物與EVA及PET相容之反應機制。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.

[反應式4]

Figure 02_image013
[Reaction 4]
Figure 02_image013

以上說明了本發明回收再製PET與EVA之複合材料母粒的配方及其材料熔融混煉相容之反應機制。以下說明本發明複合材料母粒之製法及其應用方法。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.

本發明回收再製PET與EVA之複合材料母粒之製法的步驟包括:The present invention recycles the steps of the preparation method of the composite material master batch of PET and EVA comprising:

膠料熔融步驟:利用失重式(loss-in-weight )計量系統,將乙烯-醋酸乙烯共聚物(EVA)、相容劑及聚對苯二甲酸乙二酯(PET)按比例分別下料形成高分子合膠,使用雙螺桿押出機於溫度為160-245℃以及平均剪切速率為100-300/秒(sec-1 )條件下,將該高分子合膠以100-250kg/hr之押出量押出成條狀,同時控制螺桿於押出高分子合膠的過程中在前述溫度範圍內先升溫再降溫;Melting step of rubber compound: Using a loss-in-weight metering system, ethylene-vinyl acetate copolymer (EVA), compatibilizer and polyethylene terephthalate (PET) are separately formed in proportions. The polymer composite glue is extruded at a rate of 100-250kg/hr using a twin-screw extruder at a temperature of 160-245°C and an average shear rate of 100-300/second (sec -1 ). It 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 adhesive;

半成品抽條步驟:控制該雙螺桿押出機將壓出成條狀之該高分子合膠抽條,並引導該條狀高分子合膠經過水道進行冷卻;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;

切割造粒步驟:控制該雙螺桿押出機將冷卻的條狀高分子合膠切割成粒狀後進行震動過篩,製得該複合材料母粒。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.

於本發明實施例,在該熔融膠料步驟中,該螺桿於押出高分子合膠的過程中,係從入料開始以依序以160、180、190、200、220、230、240、245、240、235℃之溫度對該高分子合膠進行先升溫再降溫之分段加熱。藉此,透過後述溫度加熱段的控制,以保證EVA裂解之前(270℃),在熔融段使PET、EVA及環氧官能化EVA達到初步反應,避免EVA裂解與環氧官能化EVA產生環氧開環自聚反應,導致r-PET與EVA無法形成均勻的高分子合膠,最終造成破壞r-PET / EVA合膠的發泡均勻性。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 PET, EVA and epoxy-functionalized EVA reach a preliminary reaction in the melting section before EVA cracking (270 ° C), 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 adhesive, which eventually destroys the foaming uniformity of the r-PET/EVA adhesive.

於本發明實施例中,本發明回收再製PET與EVA之複合材料母粒之製法中還包括在切割造粒步驟之後進行收集裝袋步驟,其係將過篩後之粒狀高分子合膠(即該複合材料母粒)收集裝袋。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.

本發明經前述配比、製法製成之複合材料母粒主要應用於鞋材製造領域,但不限於此。於本發明實施例中,該複合材料母粒係用於和乙烯-醋酸乙烯共聚物(EVA)、熱塑性彈性材料混合,以經由發泡成型技術製成鞋材。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.

本發明複合材料母粒用於鞋材製造之方法,其方法步驟包括:The composite material master batch of the present invention is used for the method of shoe material manufacture, and its method steps comprise:

取材步驟:提供乙烯-醋酸乙烯共聚物(EVA)、相容劑以及自廢棄包裝材與紡織品回收後再製之聚對苯二甲酸乙二酯再生材料(r-PET),以材料總重為100wt%計,該聚對苯二甲酸乙二酯再生材料的含量範圍為25-65wt%,該乙烯-醋酸乙烯共聚物的含量範圍為30-70wt%,該相容劑的含量範圍為2-10wt%;Material acquisition steps: Provide ethylene-vinyl acetate copolymer (EVA), compatibilizer, and recycled polyethylene terephthalate (r-PET) recycled from waste packaging materials and textiles. The total weight of the material is 100wt %, the content range of the polyethylene terephthalate regenerated material is 25-65wt%, the content range of the ethylene-vinyl acetate copolymer is 30-70wt%, and the content range of the compatibilizer is 2-10wt% %;

膠料熔融步驟:利用失重式(loss-in-weight )計量系統,將乙烯-醋酸乙烯共聚物(EVA)、相容劑及聚對苯二甲酸乙二酯(PET)按比例分別下料形成高分子合膠,使用雙螺桿押出機於溫度為160-245℃以及平均剪切速率為100-300/秒(sec-1 )條件下,將該高分子合膠以100-250kg/hr之押出量押出成條狀,同時控制螺桿於押出高分子合膠的過程中在前述溫度範圍內,從入料開始以依序以160、180、190、200、220、230、240、245、240、235℃之溫度對該高分子合膠進行先升溫再降溫之分段加熱;Melting step of rubber compound: Using a loss-in-weight metering system, ethylene-vinyl acetate copolymer (EVA), compatibilizer and polyethylene terephthalate (PET) are separately formed in proportions. The polymer composite glue is extruded at a rate of 100-250kg/hr using a twin-screw extruder at a temperature of 160-245°C and an average shear rate of 100-300/second (sec -1 ). It is extruded into strips, and at the same time, the screw is controlled within the aforementioned temperature range during the process of extruding the polymer compound glue. At a temperature of 235°C, the polymer glue is heated in stages by first heating up and then cooling down;

半成品抽條步驟:控制該雙螺桿押出機將壓出成條狀之該高分子合膠抽條,並引導該條狀高分子合膠經過水道進行冷卻;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;

切割造粒步驟:控制該雙螺桿押出機將冷卻的條狀高分子合膠切割成粒狀後進行震動過篩,製得該複合材料母粒;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;

發泡模具微調步驟:根據預設鞋材尺寸,調整發泡模具之模穴的長度、寬度及/或高度尺寸,其中,長度的微調範圍為5-10mm,寬度的微調範圍為5-10mm,厚度的微調範圍為10-20mm;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, and the fine-tuning range of the width is 5-10mm, The fine-tuning range of thickness is 10-20mm;

發泡成型步驟:將該複合材料母粒及乙烯-醋酸乙烯共聚物(EVA)、彈性材料混合後入模,經發泡成型技術製得該鞋材。Foaming molding step: the composite master batch, 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.

以下說明本發明含回收寶特瓶或漁網再製PET之複合材料母粒及其製法與發泡鞋材之應用的具體實施方式。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.

本發明複合材料母粒之聚對苯二甲酸乙二酯(PET)可取自廢棄寶特瓶。其中,聚對苯二甲酸乙二酯(PET)取自廢棄寶特瓶時,其係經由已知的寶特瓶回收技術(PET bottle recycling)製成該聚對苯二甲酸乙二酯再生材料(r-PET)。具體地,廢棄寶特瓶的處理方法包括:破碎、洗滌、分離和乾燥;其中,破碎步驟係將材料切碎成小碎片,接著,將留在該些碎片上的少許原始物質殘留物,如碎紙標籤和塑料蓋等,將該些殘留物以適合的方法除去後,進行洗滌、分離和乾燥,最終製成純PET碎片或PET薄片,形成本發明聚對苯二甲酸乙二酯再生材料(r-PET)。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 shred the material into small pieces, and then, a little residue of the original material 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).

本發明複合材料母粒之材料配比組成如下[表1]之實施例1-4所示。The material ratio composition of the composite material masterbatch of the present invention is shown in Examples 1-4 of [Table 1] below.

[表1](實施例1-4以複合材料母粒總量為100wt%計,材料含量單位以wt%計) 實施例 PET含量 EVA含量 相容劑含量 1 25 70 5 2 25 65 10 3 65 30 5 4 65 25 10 [Table 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%) Example PET content EVA content Compatibilizer content 1 25 70 5 2 25 65 10 3 65 30 5 4 65 25 10

如下列[表2]、[表3]及圖1至圖4所示,本發明含回收再製PET之複合材料母粒用於製備發泡鞋材時,本發明含回收再製PET之複合材料母粒在發泡製程中的膨脹率較習知EVA材料的膨脹率更大。如圖1所示,本發明複合材料母粒於原尺寸模具中發泡製成之片材外觀,明顯外形不規則且線條變形,藉此,本發明經以圖2所示之T型模反復測試不同結構的產品,並進行測試對比,確定本發明含回收再製PET之複合材料母粒在發泡製程中的膨脹率較習知EVA材料的膨脹率更大,是以,使用本發明含聚對苯二甲酸乙二酯再生材料(r-PET)之複合材料母粒製造發泡鞋材時,需調整模具之模穴尺寸,以提高發泡產品之外觀良率。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 determined that the expansion rate of the composite material masterbatch containing recycled PET in the foaming process is larger than the expansion rate of the conventional EVA material. When the composite material masterbatch of ethylene terephthalate (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.

[表2]

Figure 02_image015
[Table 2]
Figure 02_image015

[表2]顯示含回收再製PET之複合材料母粒在模穴厚度為8mm時長度和寬度較接近標準的長度和寬度,厚度比標準膨脹率增加15%。從不同階梯分析對比來看,需新開模具時,如模穴厚度6mm以上,長度需比原使用材料降低4%膨脹率,寬度也需調降3至4%,厚度建議比原使用材料降低10%至20%。產品尺寸以厚度為基準進行計算。[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.

[表3] 原料類別 測量點 Z軸即寬度(MM) X軸即厚度(MM) RPET料 第一 17.0 221 用修正後的模具所射 第二 16.5 221 第三 16.3 219 EVA料 第一 16.7 220 原有模具及EVA料 第二 16.3 220 第三 16.0 219 結論:修正過後的模具同原有模具用EVA料的Z和X軸資料接近。 [table 3] Raw material category Measuring point Z axis is width (MM) X-axis is thickness (MM) RPET material First 17.0 221 Shot with the revised mold second 16.5 221 third 16.3 219 EVA material First 16.7 220 Original mold and EVA material second 16.3 220 third 16.0 219 Conclusion: The modified mold is close to the Z and X axis data of the original mold EVA material.

如[表3]所示,本發明透過一系列測試,找出含聚對苯二甲酸乙二酯再生材料(r-PET)之複合材料母粒和習知EVA材料的差異性,經過T型模具和原料配方來調整,將本發明複合材料母粒影響發泡產品之寬度和厚度修進模具內,通過如圖3、圖4之試片模的測試,證明修訂模具後,本發明複合材料母粒所生產的發泡鞋材產品(圖4)可以和習知EVA材料生產的發泡產品(圖3)尺寸一樣。As shown in [Table 3], the present invention finds out the difference between the composite 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).

none

圖1係顯示使用聚對苯二甲酸乙二酯再生材料(r-PET)於原尺寸模具中發泡製成之片材外觀; 圖2係以本發明含聚對苯二甲酸乙二酯再生材料(r-PET)之複合材料母粒製成之T型模外觀; 圖3係顯示使用EVA材料於原尺寸模具中發泡製成之片材外觀; 圖4係顯示使用聚對苯二甲酸乙二酯再生材料(r-PET)於修正尺寸模具中發泡製成之片材外觀。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 the T-shaped mold made from the composite material masterbatch containing polyethylene terephthalate recycled material (r-PET) according to the present invention; Figure 3 shows the appearance of a sheet foamed in a full-scale mold using EVA material; Figure 4 shows the appearance of a sheet foamed in a modified size mold using recycled polyethylene terephthalate (r-PET).

Figure 109120420-A0101-11-0002-1
Figure 109120420-A0101-11-0002-1

Claims (10)

一種含回收再製PET之複合材料母粒,包括: 聚對苯二甲酸乙二酯(PET),係自廢棄包裝材或紡織品回收後再製之聚對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 相容劑; 其中,以該複合材料母粒之總重為100wt%計,該聚對苯二甲酸乙二酯的含量範圍為25-65wt%,該乙烯-醋酸乙烯共聚物的含量範圍為30-70wt%,該相容劑的含量範圍為2-10wt%。A composite material masterbatch containing recycled PET, comprising: Polyethylene terephthalate (PET), which is recycled polyethylene terephthalate (r-PET) made from waste packaging materials or textiles; Ethylene Vinyl Acetate (EVA); and Compatibilizer; Wherein, based on the total weight of the composite master batch as 100wt%, the content range of the polyethylene terephthalate is 25-65wt%, and the content range of the ethylene-vinyl acetate copolymer is 30-70wt%, The content of the compatibilizer ranges from 2 to 10 wt%. 如申請專利範圍第1項所述之含回收再製PET之複合材料母粒,其中,該聚對苯二甲酸乙二酯再生材料(r-PET)之固有黏度(Intrinsic Viscosity,IV)為0.6-1.0 dL/g。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- 1.0 dL/g. 如申請專利範圍第1項所述之含回收再製PET之複合材料母粒,其中,該乙烯-醋酸乙烯共聚物(EVA)之醋酸乙烯酯(VA)的含量為8-40wt%,該乙烯-醋酸乙烯共聚物之熔體流動速率(Melt mass-flow rate,MFR)在190℃/2.16kg之條件下為每10分鐘1-10 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 vinyl acetate copolymer is 1-10 g per 10 minutes at 190°C/2.16 kg. 如申請專利範圍第1項所述之含回收再製PET之複合材料母粒,其中,該相容劑係選自甲基丙烯酸縮水甘油酯(GMA)、順丁烯二酸酐(MA)、丙烯酸(AA)、含有一級胺官能基團的接枝高分子、含有二級胺官能基團的接枝高分子或者含有異氰酸酯的接枝高分子。The composite material masterbatch containing recycled PET as described in item 1 of the patent application scope, wherein the compatibilizer is selected from the group consisting of glycidyl methacrylate (GMA), maleic anhydride (MA), acrylic acid ( AA), a grafted polymer containing a primary amine functional group, a grafted polymer containing a secondary amine functional group, or a grafted polymer containing an isocyanate. 一種含回收再製PET之複合材料母粒之製法,其中,該製法步驟包括: 取材步驟:提供乙烯-醋酸乙烯共聚物(EVA)、相容劑以及自廢棄包裝材或紡織品回收後再製之聚對苯二甲酸乙二酯再生材料(r-PET),以材料總重為100wt%計,該聚對苯二甲酸乙二酯再生材料的含量範圍為25-65wt%,該乙烯-醋酸乙烯共聚物的含量範圍為30-70wt%,該相容劑的含量範圍為2-10wt%; 膠料熔融步驟:利用失重式(loss-in-weight )計量系統,將乙烯-醋酸乙烯共聚物(EVA)、相容劑及聚對苯二甲酸乙二酯(PET)按比例分別下料形成高分子合膠,使用雙螺桿押出機於溫度為160-245℃以及平均剪切速率為100-300/秒(sec-1 )條件下,將該高分子合膠以100-250kg/hr之押出量押出成條狀,同時控制螺桿於押出高分子合膠的過程中在前述溫度範圍內先升溫再降溫; 半成品抽條步驟:控制該雙螺桿押出機將壓出成條狀之該高分子合膠抽條,並引導該條狀高分子合膠經過水道進行冷卻; 切割造粒步驟:控制該雙螺桿押出機將冷卻的條狀高分子合膠切割成粒狀後進行震動過篩,製得該複合材料母粒。A method for producing a composite material masterbatch containing recycled PET, wherein the steps of the production method include: a step of obtaining materials: providing ethylene-vinyl acetate copolymer (EVA), a compatibilizer, and a polyolefin that is 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 of the polyethylene terephthalate recycled material is in the range of 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%; Rubber material melting step: using a loss-in-weight metering system, ethylene-vinyl acetate copolymer (EVA) , compatibilizer and polyethylene terephthalate (PET) are separately 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 (sec -1 ), extrude the polymer glue into strips at an extrusion rate of 100-250kg/hr, and control the screw 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. 如申請專利範圍第5項所述之含回收再製PET之複合材料母粒之製法,其熔融膠料步驟中,該螺桿於押出高分子合膠的過程中,係從入料開始以依序以160、180、190、200、220、230、240、245、240、235℃之溫度對該高分子合膠進行先升溫再降溫之分段加熱。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. 如申請專利範圍第6項所述之含回收再製PET之複合材料母粒之製法,其中: 該聚對苯二甲酸乙二酯再生材料(r-PET)之固有黏度(Intrinsic Viscosity,IV)為0.6-1.0 dL/g; 該乙烯-醋酸乙烯共聚物(EVA)之醋酸乙烯酯(VA)的含量為8-40wt%,該乙烯-醋酸乙烯共聚物之熔體流動速率(Melt mass-flow rate,MFR)在190℃/2.16kg之條件下為每10分鐘1-10 g。As described in item 6 of the patent application scope, the method for producing composite material masterbatch containing recycled PET, wherein: The intrinsic viscosity (IV) of the polyethylene terephthalate recycled material (r-PET) is 0.6-1.0 dL/g; The vinyl acetate (VA) content of the ethylene-vinyl acetate copolymer (EVA) is 8-40wt%, and the melt flow rate (MFR) of the ethylene-vinyl acetate copolymer is at 190°C/ Under the condition of 2.16kg, it is 1-10 g every 10 minutes. 如申請專利範圍第6項所述之含回收再製PET之複合材料母粒之製法,其中,該相容劑係選自甲基丙烯酸縮水甘油酯(GMA)、順丁烯二酸酐(MA)、丙烯酸(AA)、含有一級胺官能基團的接枝高分子、含有二級胺官能基團的接枝高分子或者含有異氰酸酯的接枝高分子。The method for preparing composite material masterbatch containing recycled PET as described in item 6 of the patent application scope, wherein 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. 一種含回收再製PET之複合材料母粒於鞋材製造之應用方法,其方法步驟包括: 取材步驟:提供乙烯-醋酸乙烯共聚物(EVA)、相容劑以及自廢棄包裝材或紡織品回收後再製之聚對苯二甲酸乙二酯再生材料(r-PET),以材料總重為100wt%計,該聚對苯二甲酸乙二酯再生材料的含量範圍為25-65wt%,該乙烯-醋酸乙烯共聚物的含量範圍為30-70wt%,該相容劑的含量範圍為2-10wt%; 膠料熔融步驟:利用失重式(loss-in-weight )計量系統,將乙烯-醋酸乙烯共聚物(EVA)、相容劑及聚對苯二甲酸乙二酯(PET)按比例分別下料形成高分子合膠,使用雙螺桿押出機於溫度為160-245℃以及平均剪切速率為100-300/秒(sec-1 )條件下,將該高分子合膠以100-250kg/hr之押出量押出成條狀,同時控制螺桿於押出高分子合膠的過程中在前述溫度範圍內,從入料開始以依序以160、180、190、200、220、230、240、245、240、235℃之溫度對該高分子合膠進行先升溫再降溫之分段加熱; 半成品抽條步驟:控制該雙螺桿押出機將壓出成條狀之該高分子合膠抽條,並引導該條狀高分子合膠經過水道進行冷卻; 切割造粒步驟:控制該雙螺桿押出機將冷卻的條狀高分子合膠切割成粒狀後進行震動過篩,製得該複合材料母粒; 發泡模具微調步驟:根據預設鞋材尺寸,調整發泡模具之模穴的長度、寬度及/或高度尺寸,其中,長度的微調範圍為5-10mm,寬度的微調範圍為5-10mm,厚度的微調範圍為10-20mm; 發泡成型步驟:將該複合材料母粒及乙烯-醋酸乙烯共聚物(EVA)、彈性材料混合後入模,經發泡成型技術製得該鞋材。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 range of the polyethylene terephthalate recycled material is 25-65wt%, 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 mixed (EVA), compatibilizer and polyethylene terephthalate (PET) are separately 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 the 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 composite 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 masterbatch; Step of fine-tuning 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; Foaming 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. 如申請專利範圍第9項所述之含回收再製PET之複合材料母粒於鞋材製造之應用方法,其中: 該聚對苯二甲酸乙二酯再生材料(r-PET)之固有黏度(Intrinsic Viscosity,IV)為0.6-1.0 dL/g; 該乙烯-醋酸乙烯共聚物(EVA)之醋酸乙烯酯(VA)的含量為8-40wt%,該乙烯-醋酸乙烯共聚物之熔體流動速率(Melt mass-flow rate,MFR)在190℃/2.16kg之條件下為每10分鐘1-10 g; 該相容劑係選自甲基丙烯酸縮水甘油酯(GMA)、順丁烯二酸酐(MA)、丙烯酸(AA)、含有一級胺官能基團的接枝高分子、含有二級胺官能基團的接枝高分子或者含有異氰酸酯的接枝高分子。As described in item 9 of the scope of the patent application, the application method of composite material masterbatch containing recycled PET in shoe material manufacturing, wherein: The intrinsic viscosity (IV) of the polyethylene terephthalate recycled material (r-PET) is 0.6-1.0 dL/g; The vinyl acetate (VA) content of the ethylene-vinyl acetate copolymer (EVA) is 8-40wt%, and the melt flow rate (MFR) of the ethylene-vinyl acetate copolymer is at 190°C/ 1-10 g every 10 minutes under the condition of 2.16kg; The compatibilizer is selected from glycidyl methacrylate (GMA), maleic anhydride (MA), acrylic acid (AA), graft polymers containing primary amine functional groups, and secondary amine functional groups The grafted polymer or the grafted polymer containing isocyanate.
TW109120420A 2020-06-17 2020-06-17 Composite masterbatch for manufacturing pet by recycling beverage cans and its preparation method and application of foaming shoe material TWI755759B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
TW109120420A TWI755759B (en) 2020-06-17 2020-06-17 Composite masterbatch for manufacturing pet by recycling beverage cans and its preparation method and application of foaming shoe material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW109120420A TWI755759B (en) 2020-06-17 2020-06-17 Composite masterbatch for manufacturing pet by recycling beverage cans and its preparation method and application of foaming shoe material

Publications (2)

Publication Number Publication Date
TW202200334A true TW202200334A (en) 2022-01-01
TWI755759B TWI755759B (en) 2022-02-21

Family

ID=80787910

Family Applications (1)

Application Number Title Priority Date Filing Date
TW109120420A TWI755759B (en) 2020-06-17 2020-06-17 Composite masterbatch for manufacturing pet by recycling beverage cans and its preparation method and application of foaming shoe material

Country Status (1)

Country Link
TW (1) TWI755759B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI829246B (en) * 2022-07-15 2024-01-11 匯智綠材科技股份有限公司 Foam material composition, foam material and method for producing the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104341741A (en) * 2013-07-30 2015-02-11 青岛欣展塑胶有限公司 High performance low cost PET (polyethylene terephthalate)/PBT (polybutylene terephthalate) alloy and preparation method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI829246B (en) * 2022-07-15 2024-01-11 匯智綠材科技股份有限公司 Foam material composition, foam material and method for producing the same

Also Published As

Publication number Publication date
TWI755759B (en) 2022-02-21

Similar Documents

Publication Publication Date Title
WO2022011542A1 (en) Composite masterbatch formed by recycling pet plastic bottles and reproducing pet, preparation method, and application of foamed shoe material
US20060086836A1 (en) Rubber and plastic bonding
CN1890307A (en) Expanded particulate moulded parts consisting of expandable polystyrenes and mixtures of thermoplastic polymers
US20030092793A1 (en) Process for the preparation of biodegradable resin
TW202244117A (en) Polyester resin composition for injection molding, manufacturing method and injection molded product thereof
CN113736129A (en) Lignin-containing biodegradable polyester composite bead foaming material with high crystallization rate and preparation method thereof
TWI755759B (en) Composite masterbatch for manufacturing pet by recycling beverage cans and its preparation method and application of foaming shoe material
CN114989581B (en) Biodegradable polylactic acid foaming particle and preparation method thereof
CN106751358B (en) Granulation method of granules for coating film, granules and application thereof
CN112940425A (en) High-temperature water-soluble PVA composition for blow molding and particles and film thereof
US20220041857A1 (en) Composite Masterbatch Granules Containing Reprocessed Polyethylene Terephthalate (PET) Derived from Recycled Pet Bottles, Method for Making the Same, and Use of the Same in Foamed Shoe Material
CN113912874B (en) Recycled PET plastic bottle remanufactured PET composite material master batch, preparation method and application of foamed shoe material
CN109721928B (en) Polypropylene composition and preparation method and application thereof
US3706699A (en) Manufacture of moulding material starting from polyethylene terephthalate
US11447617B2 (en) Recycling of polymer materials
CN114957978A (en) Method for recycling fishing net nylon 6 through granulating machine and recycled fishing net nylon 6
JP3126907B2 (en) Method for producing thermoplastic polyester resin foam molded article
CN111356726A (en) Method for producing low density polyester foam from low intrinsic viscosity polyester feedstock and articles made therefrom
JP4125942B2 (en) Mixed material using plastic waste, manufacturing apparatus thereof, and manufacturing method thereof
CN109294087B (en) Modified polystyrene material and preparation method thereof
JPH05301222A (en) Method for recycling plastic products
US20230347553A1 (en) Method for Making Foamed Shoe Material
WO1995033002A1 (en) Process for reclaiming crosslinked acrylic scrap
CN114456532A (en) TPE-KM6 modified material and production process thereof
JP3217091B2 (en) Reshaped product containing liquid crystal polymer