CN113912874B - 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 PDFInfo
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Abstract
本发明提供一种回收PET塑料瓶再制PET复合材料母粒及制法与发泡鞋材的应用,其中,所述复合材料母粒及其制法,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,利用高扭力押出机制成复合材料母粒;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
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:
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:
其中,化学式1的n=100mole。
化学式2:
其中,化学式2中,m+n=100mol%时,m=60-84mol%,n=16-40mol%。
化学式3:
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:
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:
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:
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:
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)
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
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。
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 (2)
1.一种回收PET塑料瓶再制PET复合材料母粒用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:提供由乙烯-醋酸乙烯共聚物、环氧官能化EVA以及自废弃PET塑料瓶回收后再制的聚对苯二甲酸乙二酯再生材料组成的母粒原料,以所述母粒原料总重为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%,所述环氧官能化EVA的含量范围为2-10wt%;其中,所述聚对苯二甲酸乙二酯再生材料、所述乙烯-醋酸乙烯共聚物以及所述环氧官能化EVA依序具有如下化学式1、化学式2以及化学式3的结构:
,
化学式1
其中,化学式1的n=100 mole;
,
化学式2
其中,化学式2中,m+n=100 mol%时,m=60-84mol%,n=16-40mol%;以及
,
化学式3
其中,化学式3中,x+y+z=100mol%时,x=45-80mol%,y=5-30mol%,z=5-26mol%;
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、环氧官能化EVA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、热塑性弹性材料混合后入模,经发泡成型技术制得所述鞋材。
2.根据权利要求1所述的回收PET塑料瓶再制PET复合材料母粒用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0.6-1.0 dL/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1-10 g。
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