CN101805516B - 利用废渔网制备的尼龙6切片及其制备方法 - Google Patents

利用废渔网制备的尼龙6切片及其制备方法 Download PDF

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CN101805516B
CN101805516B CN2010101259636A CN201010125963A CN101805516B CN 101805516 B CN101805516 B CN 101805516B CN 2010101259636 A CN2010101259636 A CN 2010101259636A CN 201010125963 A CN201010125963 A CN 201010125963A CN 101805516 B CN101805516 B CN 101805516B
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nylon
fishing net
slice
waste fishing
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黄志杰
陈佰全
杨丰富
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CGN JUNER NEW MATERIALS CO., LTD.
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Shanghai Jun'er New Material Co Ltd
JUNER NEW MATERIALS CO Ltd ZHEJIANG
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/918Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
    • B29C48/9185Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05Filamentary, e.g. strands
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92904Die; Nozzle zone

Abstract

本发明公开了一种利用废渔网制备的尼龙6切片,其原料的重量百分比组成为:废渔网95%-98%,扩链剂0.5%-1.0%,复合热稳定剂1.0%-3.0%,润滑剂0.5%-1.0%。该尼龙6切片具有与PA6新料切片相当的力学性能和流动加工性能,颜色浅,杂质少,可以部分或全部代替尼龙6新料切片用于纺丝或改性工程塑料等原材料,减少了环境污染、实现了资源循环利用,具有极大的社会效应和经济效益。

Description

利用废渔网制备的尼龙6切片及其制备方法
技术领域
[0001] 本发明涉及高分子材料领域,尤其涉及的是一种利用废渔网制备的尼龙6切片及其制备方法。
背景技术
[0002] 我国海岸线漫长,内陆江流湖泊众多,捕鱼、水产养殖业十分普遍,每年需使用大量的渔网,同时也有许多废烂渔网被丢弃。渔网基本由尼龙6纺丝后编制而成,随意丢弃后,无法在短时间内降解,对环境和水生动植物带来极大危害。
[0003] 尼龙6 (简称PA6),由己内酰胺聚合而成,是石油工业的最终产品,也是5大通用工程塑料中产量最大、品种最多、用途最广、综合性能优良的一类基础树脂。工程用尼龙6其分子量一般在1. 5万-3万之间,具有很好的机械强度,软化点高,耐热,耐油,耐弱酸,耐碱和一般溶剂,电绝缘性好,无毒,无臭,耐候,染色性好,磨擦系数低,同时具有优良的加工成型特性。其中用于纺丝的PA6 —般相对粘度为2. 4左右,相对分子量在1. 5-2万之间,具有很好的流动性。
[0004] 随着石油资源的日益稀缺和国际油价受政治经济因素的影响,合成塑料树脂价格日益提升,加之人们环境意识的不断提高,塑料的循环利用越来越受到各国重视。由于废弃渔网丝其长期浸泡于水中,受外界阳光、盐、微生物等作用,分子链发生了不同程度的降解、 断裂,当其相对分子量降低至10000以下时,PA6作为工程塑料将失去基本的使用价值。另外,由于水中使用的特殊环境,渔网丝上通常粘附有大量的泥沙、水草、贝壳等杂质,这些杂质也给PA6的回收应用带来许多困难。不加处理直接回收得到的尼龙6切片分子量低、杂质多、颜色深,力学性能和外观均无法满足基本使用要求。
发明内容
[0005] 本发明提供了一种利用废渔网制备的尼龙6切片,具有优异的性能,可代替PA6新料切片用作纺丝或改性工程塑料的原材料。
[0006] 一种利用废渔网制备的尼龙6切片,其原料的重量百分比组成为:
[0007]废渔网 95%-98%
[0008]扩链剂 0.5%-1.0%
[0009] 复合热稳定剂 1.0%-3.0%
[0010]润滑剂 0.5%-1.0%。
[0011] 所述的废渔网为废弃的由尼龙6纺丝编制的渔网。
[0012] 所述的扩链剂选用二恶唑啉、环氧基苯乙烯-丙烯酸酯低聚物中的一种或两种, 可选用市售产品,扩链剂的作用在于将低分子量的PA6分子重新连结起来,起到提高分子量的作用。
[0013] 所述的复合热稳定剂选用市售的碘化亚铜、受阻酚类稳定剂(如抗氧剂1098)、亚磷酸酯类稳定剂(如抗氧剂168)中的至少两种类型的稳定剂,这种复合热稳定剂能防止PA6在生产过程中的氧化变黄,同时提高产品的耐热性。
[0014] 所述的润滑剂选用市售硬脂酸镁、聚酯型润滑剂(如霍尼韦尔的ACM0)的一种或两种,其能改善PA6在加工性能,降低加工能耗。
[0015] 所述的尼龙6切片的制备方法,包括以下步骤:
[0016] (1)将回收的废渔网破碎成直径小于IOmm的碎片,将碎片经洗涤除去泥沙并离心甩干后干燥至水分含量低于0.2% (重量百分比);
[0017] (2)将上述干燥好的废渔网碎片与扩链剂、复合热稳定剂和润滑剂混合均勻,加入到双螺杆挤出机中挤出后经过水冷、切粒,制得尼龙6切片;
[0018] 其中,双螺杆挤出机由进料段到机头的温度依次为:240°C -250240°C _250°C、 240 °C -250 °C >240 °C -250 °C >225 °C _235°C、215°C _225°C、215°C -225 °C >205 °C _215°C,模头的温度为230°C -240°C。
[0019] 挤出机前四段温度高于PA6的熔点能加快材料的塑化,并迅速与各种助剂达到分子级别的混合,同时促进扩链剂与低分子PA6的反应,此后几区逐渐降低温度,可避免PA6 分子在高温下重新降解。
[0020] 所述的双螺杆挤出机的模头安装有800目金属过滤网,这能有效过滤渔网丝中未彻底清洗干净的固体杂质,提高产品纯度。
[0021] 所述的双螺杆挤出机选用本领域常用的通用设备即可。
[0022] 本发明具有如下有益效果:
[0023] 本发明利用废渔网制备的PA6切片,具有与PA6新料切片(即直接利用己内酰胺为原料聚合的PA6切片)相当的力学性能和流动加工性能,颜色浅,杂质少,可部分或全部代替PA6新料切片用作纺丝和改性工程塑料等的原材料。
[0024] 本发明将废弃物进行再利用,减少了环境污染、实现了资源循环利用,具有极大的社会效应和经济效益。
[0025] 本发明制备方法操作简单,无需特殊的设备,成本低,适于工业化生产。 附图说明
[0026] 图1是本发明PA6切片的一种工艺流程图。
具体实施方式
[0027] 实施例1
[0028] 将回收的废渔网加入高速破碎机中破碎为直径小于IOmm的碎片,然后倒入大型滚筒水洗机中洗去泥沙并离心甩干,随后使用料斗式烘箱将其干燥至水分含量为0. 2% (重量百分比)。
[0029] 将98Kg上述干燥好的废渔网碎片与0. 5Kg 二恶唑啉、0. 5Kg受阻酚类稳定剂:抗氧剂1098 (雅宝)、0. 5Kg亚磷酸酯类稳定剂:抗氧剂168 (雅宝)和0. 5Kg硬脂酸镁在高速混合机中高速混合anin后,从第一加料器(主喂料)加入模头安装有800目金属过滤网的双螺杆挤出机中,双螺杆挤出机由进料段到机头的温度依次为:245°C、245°C、245°C、 235°C、230°C、220°C、220°C、210°C,模头的温度为235°C,挤出后经过水冷、切粒,然后包装, 制得PA6切片。[0030] 实施例2
[0031] 按实施例1中的处理方式将回收的废渔网处理达到要求后,将98Kg上述干燥好的废渔网碎片与0. 5Kg环氧基苯乙烯-丙烯酸酯低聚物、0. 5Kg受阻酚受阻酚类稳定剂: 抗氧剂1098 (雅宝)、0. 5Kg亚磷酸酯类稳定剂:抗氧剂168 (雅宝)和0. 5Kg聚酯润滑剂 AC540 (霍尼韦尔)在高速混合机中高速混合aiiin后,从第一加料器(主喂料)加入模头安装有800目金属过滤网的双螺杆挤出机中,双螺杆挤出机由进料段到机头的温度依次为: 245"C、245"C、245"C、235"C、230"C、220°C、220°C、210°C,模头的温度为 2;35"C,挤出后经过水冷、切粒,然后包装,制得PA6切片。
[0032] 实施例3
[0033] 按实施例1中的处理方式将回收的废渔网处理达到要求后,将95Kg上述干燥好的废渔网碎片与0. 5Kg 二恶唑啉、0. 5Kg环氧基苯乙烯-丙烯酸酯低聚物、1. 5Kg受阻酚类稳定剂:抗氧剂1098 (雅宝)、1. OKg亚磷酸酯类稳定剂:抗氧剂168 (雅宝)、0. 5KG碘化亚铜和0. 5Kg硬脂酸镁、0. 5Kg聚酯润滑剂AC540 (霍尼韦尔)在高速混合机中高速混合aiiin 后,从第一加料器(主喂料)加入模头安装有800目金属过滤网的双螺杆挤出机中,双螺杆挤出机由进料段到机头的温度依次为:245V、245°C、245°C、235°C、230°C、220°C、220°C、 210°C,模头的温度为235°C,挤出后经过水冷、切粒,然后包装,制得PA6切片。
[0034] 将上述PA6切片粒料在鼓风干燥箱中于110°C放置4小时,然后由注射成型机制备
成测试样条,进行性能测试,结果见下表:
[0035]
Figure CN101805516BD00051
[0036] 注:表中的对比材料1为不加任何处理的废渔网丝脆片。
[0037] 对比材料2为广州新会美达生产的牌号M2400H的PA6切片。[0038] 结论:从上述测试数据可看出,本发明的尼龙6切片具有与PA6新料切片相当的力学性能和流动加工性能。

Claims (3)

1.一种利用废渔网制备的尼龙6切片,其原料的重量百分比组成为废渔网扩链剂95%-98% 0.5%-1.0% 1.0%-3.0% 0.5%-1.0%复合热稳定剂润滑剂所述的废渔网为废弃的由尼龙6纺丝编织的渔网;所述的扩链剂为二噁唑啉、环氧基苯乙烯-丙烯酸酯低聚物中的一种或两种; 所述的复合热稳定剂为碘化亚铜、受阻酚稳定剂、亚磷酸酯稳定剂中的至少两种; 所述的润滑剂为硬脂酸镁、聚酯型润滑剂中的一种或两种。
2.如权利要求1所述的尼龙6切片的制备方法,其特征在于,包括以下步骤:(1)将回收的废渔网破碎成直径小于IOmm的碎片,将碎片经洗涤除去泥沙并离心甩干后干燥至水分含量低于0. 2% ;(2)将上述干燥好的废渔网碎片与扩链剂、复合热稳定剂和润滑剂混合均勻,加入到双螺杆挤出机中挤出后经过水冷、切粒,制得尼龙6切片;其中,双螺杆挤出机由进料段到机头的温度依次为:240°C -250240°C _250°C、 240 °C -250 °C >240 °C -250 °C >225 °C _235°C、215°C _225°C、215°C -225 °C >205 °C _215°C,模头的温度为230°C -240°C。
3.如权利要求2所述的制备方法,其特征在于,所述的双螺杆挤出机的模头安装有800 目金属过滤网。
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