CN106336555A - 一种改性再生聚乙烯护套料及其制备方法 - Google Patents
一种改性再生聚乙烯护套料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种改性再生聚乙烯护套料,包括下列重量份的组分:再生聚乙烯护套料80‑90份,再生聚乙烯功能母料10‑20份,再生聚乙烯棚膜料10‑15份;其中,所述再生聚乙烯功能母料包括:再生聚乙烯地膜60‑70份,再生防雾滴棚膜20‑30份,再生聚乙烯瓶盖10‑30份,炭黑母料3‑4份和抗氧剂0.3‑0.5份。本发明提供的改性再生聚乙烯护套料,以再生聚乙烯护套料、再生聚乙烯棚膜料与功能性母料的共混料为主要原料,具有优异的物理机械性能、耐环境应力开裂性能、抗热老化性能和加工性能能满足护套使用要求,制备成本低,而且制备方法简单,可最大程度提高原料的性能。
Description
技术领域
本发明涉及高分子材料技术领域,特别涉及一种再生聚乙烯多功能母料及其制备方法。
背景技术
光缆或电缆由于铺设或使用环境的限制,需要有外防护层。外防护层的目的在于起到防水隔潮、防腐蚀、防意外损伤、甚至绝缘等保护作用。这一层外防护层就是通常所谓的“护套”,用以生产“护套”的材料,称为“护套料”。经过多年的发展,护套料已由浸渍纸(绳)等过渡到了橡塑材料,聚乙烯则因其优异的物化性能、加工性能及低廉的成本,逐渐成为目前户外光缆和电缆护套料的代表。
我国聚乙烯护套料的需求量在20万吨以上,今后随着国民建设的发展需要,市场需求量将会进一步增加,因此护套料的市场需求很大,前景非常广阔。但我国每年同样产生大量废旧护套产品,造成资源浪费和环境污染,目前废旧护套的回收主要采用焚烧或者经简单加工应用于一些低端市场领域,难以发挥其应有作用。再生聚乙烯护套经长期使用或者直接再生后存在耐热稳定性差、断裂伸长率低、性能不稳定、耐开裂性能差等,性能达不到护套使用要求,难以直接或者单独应用于护套生产。
发明内容
本发明的一个目的是提供一种以再生聚乙烯护套料、再生聚乙烯棚膜料与功能性母料的共混料为主要原料,具有优异的物理机械性能、耐环境应力开裂性能、抗热老化性能和加工性能的改性再生聚乙烯护套料以解决现有技术的不足。
本发明的另一个目的是提供一种上述改性再生聚乙烯护套料的制备方法。
本发明通过以下技术方案来实现发明目的:
一种改性再生聚乙烯护套料,包括下列重量份的组分:再生聚乙烯护套料80-90份,再生聚乙烯功能母料10-20份,再生聚乙烯棚膜料10-15份;
所述再生聚乙烯护套料密度0.943-0.953g/10cm3,熔体质量流动速率(2.16kg)0.1-0.6g/10min;
所述再生聚乙烯棚膜料密度0.918-0.923g/10cm3,熔体质量流动速率(2.16kg)0.9-1.1g/10min。
进一步地,所述再生聚乙烯功能母料由下列重量份的组分制成:再生聚乙烯地膜60-70份;再生防雾滴棚膜20-30份;再生聚乙烯瓶盖10-30份;炭黑母料3-4份;抗氧剂0.3-0.5份;消泡剂0.2-0.6份。
进一步地,所述的再生聚乙烯地膜密度为0.917~0.925g/cm3,熔体质量流动速率(2.16kg)为2.3~2.8g/10min,灰分<2%;
所述的再生防雾滴棚膜主要成分包括相对含量75%~85%的EVA和相对含量15~25%的LLDPE,灰分<2%;
所述的再生聚乙烯瓶盖密度为0.950~0.960g/cm3,熔体质量流动速率(2.16kg)为3~4g/10min,灰分<2%。
进一步地,所述的抗氧剂为受阻酚类抗氧剂和亚磷酸酯类抗氧剂的复配物,两者的重量比为1:1,所述受阻酚类抗氧剂为四[β-(3,5二叔丁基-4-羟基苯基)丙酸]季戊四醇酯或β(3,5二叔丁基—4—羟基苯基)丙酸十八醇酯;所述亚磷酸酯类抗氧剂为三(2,4-二叔丁基苯基)亚磷酸酯或双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯。
进一步地,所述抗氧剂为抗氧剂1076和抗氧剂168的混合物,所述炭黑母料中炭黑浓度为45-50%。
进一步地,所述的消泡剂为氧化钙。
上述改性再生聚乙烯护套料的制备方法,包括以下步骤:
(1)再生塑料预处理
按比例称取再生聚乙烯地膜、再生防雾滴棚膜和再生聚乙烯瓶盖,并将三种再生塑料经清洗、分离、干燥和粉碎后加入高速混合机;
(2)原料混合
按比例将炭黑母料、抗氧剂和消泡剂加入步骤(1)中的混合物中进行搅拌混合,混合条件为:搅拌转速为2000-2500转/分,搅拌时间6-10min,搅拌温度50-60℃;
(3)母料造粒
将步骤(2)中混合均匀的物料加入到双螺杆挤出机中熔融、塑化、挤出和造粒。
(4)改性专用料制备
将15-25份功能母料加入到再生聚乙烯护套料和再生聚乙烯棚膜料中,经高速混合机混匀后制得改性改性再生聚乙烯护套料。
进一步地,所述步骤(2)中抗氧剂混合前先经60℃的甲醇或者
乙醇溶解;所述步骤(3)中双螺杆挤出机的螺杆长径比为30~33;
螺杆组合中有0-3段剪切块,其中包含0-1段反向剪切块;造粒
温度为175-190℃;
所述步骤(4)中搅拌转速为1500-2000转/分,搅拌时间3-5min,搅拌温度30-40℃。
进一步地,所述步骤(3)中双螺杆挤出机的螺杆长径比为33;螺杆组合中有1段剪切块;造粒温度为180℃。
本发明提供的改性再生聚乙烯护套料,以再生聚乙烯护套料、再生聚乙烯棚膜料与功能性母料的共混料为主要原料,降低了材料成本,经济效益显著,具有较高的断裂伸长率、加工速度、优异的热稳定性及耐环境应力开裂性能等,采用的制备方法简单有效,可最大程度保持或提高原料的性能。
具体实施方式
下面结合具体实施例对本发明作进一步详细的说明。
实施例1
改性再生聚乙烯护套料,包括下列重量份的组分:再生聚乙烯护套料85份,再生聚乙烯功能母料15份,再生聚乙烯棚膜料10份;其中,再生聚乙烯功能母料包括再生聚乙烯地膜68份、再生防雾滴棚膜23份、再生聚乙烯瓶盖14份、炭黑母料3.5份、抗氧剂0.4份和氧化钙0.4份,炭黑母料浓度为48%、抗氧剂1076及抗氧剂168各0.2份。
再生聚乙烯护套料密度0.945g/cm3,熔体质量流动速率(2.16kg)0.55g/10min;再生聚乙烯棚膜料密度0.921g/10min,熔体质量流动速率((2.16kg)1.1g/10min;再生聚乙烯地膜密度为0.924g/cm3,熔体质量流动速率(2.16kg)2.6g/10min,灰分1.1%;再生防雾滴棚膜中EVA相对含量80%,LLDPE相对含量20%,灰分1.2%;再生聚乙烯瓶盖,密度为0.951g/cm3,熔体质量流动速率(2.16kg)3.9g/10min,灰分1.4%;
制备方法如下:
(1)再生塑料预处理
按上述比例称取再生聚乙烯地膜、再生防雾滴棚膜和再生聚乙烯瓶盖,并将三种再生塑料经清洗、分离、干燥和粉碎后加入高速混合机;
(2)原料混合
抗氧剂采用60℃甲醇或者乙醇溶解后,按比例将炭黑母料、抗氧剂和氧化钙加入步骤(1)中的混合物中进行搅拌混合均匀,搅拌转速为2400转/分,搅拌时间8min,搅拌温度52℃;
(3)母料造粒
将步骤(2)中混合均匀的物料加入到双螺杆挤出机中熔融、塑化、挤出和造粒,双螺杆挤出机的螺杆长径比为33,螺杆组合中有1段剪切块,造粒最高温度为190℃。
(4)改性专用料制备
将上述重量份数的再生聚乙烯功能母料加入到再生聚乙烯护套料和再生聚乙烯棚膜料中经高速混合机混匀,在30℃下以转速1500转/分搅拌3min后,制得改性再生聚乙烯护套料。
实施例2
改性再生聚乙烯护套料,包括下列重量份的组分:再生聚乙烯护套料85份,再生聚乙烯功能母料20份,再生聚乙烯棚膜料15份;其中,再生聚乙烯功能母料包括再生聚乙烯地膜68份、再生防雾滴棚膜23份、再生聚乙烯瓶盖14份、炭黑母料3.5份、抗氧剂0.5份和氧化钙0.4份,炭黑母料浓度为48%、抗氧剂1076及抗氧剂168各0.25份。
再生聚乙烯护套料密度0.945gg/cm3,熔体质量流动速率(2.16kg)0.55g/10min;再生聚乙烯棚膜料密度0.921g/10min,熔体质量流动速率((2.16kg)1.1g/10min;再生聚乙烯地膜密度为0.924g/cm3,熔体质量流动速率(2.16kg)2.6g/10min,灰分1.1%;再生防雾滴棚膜中EVA相对含量80%,LLDPE相对含量20%,灰分1.2%;再生聚乙烯瓶盖,密度为0.951g/cm3,熔体质量流动速率(2.16kg)3.9g/10min,灰分1.4%。
制备方法如下:
(1)再生塑料预处理
按上述比例称取再生聚乙烯地膜、再生防雾滴棚膜和再生聚乙烯瓶盖,并将三种再生塑料经清洗、分离、干燥和粉碎后加入高速混合机;
(2)原料混合
抗氧剂采用60℃甲醇或者乙醇溶解后,按比例将炭黑母料、抗氧剂和氧化钙加入步骤(1)中的混合物中进行搅拌混合均匀,搅拌转速为2500转/分,搅拌时间8min,搅拌温度57℃;
(3)母料造粒
将步骤(2)中混合均匀的物料加入到双螺杆挤出机中熔融、塑化、挤出和造粒,双螺杆挤出机的螺杆长径比为33,螺杆组合中有1段剪切块,造粒最高温度为180℃。
(4)改性专用料制备
将上述重量份数的再生聚乙烯功能母料加入到再生聚乙烯护套料和再生聚乙烯棚膜料中经高速混合机混匀,在30℃下以转速1600转/分搅拌3min后,制得改性再生聚乙烯护套料。
实施例3
改性再生聚乙烯护套料,包括下列重量份的组分:再生聚乙烯护套料85份,再生聚乙烯功能母料13份,再生聚乙烯棚膜料15份;其中,再生聚乙烯功能母料包括再生聚乙烯地膜68份、再生防雾滴棚膜23份、再生聚乙烯瓶盖24份、炭黑母料3.5份、抗氧剂0.5份和氧化钙0.3份,炭黑母料浓度为48%、抗氧剂1076及抗氧剂168各0.25份。
再生聚乙烯护套料密度0.945gg/cm3,熔体质量流动速率(2.16kg)0.55g/10min;再生聚乙烯棚膜料密度0.921g/10min,熔体质量流动速率((2.16kg)1.1g/10min;再生聚乙烯地膜密度为0.924g/cm3,熔体质量流动速率(2.16kg)2.4g/10min,灰分1.1%;再生防雾滴棚膜中EVA相对含量76%,LLDPE相对含量24%,灰分0.6%;再生聚乙烯瓶盖,密度为0.950g/cm3,熔体质量流动速率(2.16kg)3.2g/10min,灰分0.8%。
制备方法与实施例1的制备工艺条件完全相同。
(4)改性专用料制备
将上述重量份数的再生聚乙烯功能母料加入到再生聚乙烯护套料和再生聚乙烯棚膜料中经高速混合机混匀,在30℃下以转速1600转/分搅拌3min后,制得改性再生聚乙烯护套料。
实施例4
再生聚乙烯护套料,包括下列重量份的组分:再生聚乙烯护套料90份,再生聚乙烯功能母料10份,再生聚乙烯棚膜料10份;其中,再生聚乙烯功能母料包括再生聚乙烯地膜62份、再生防雾滴棚膜28份、再生聚乙烯瓶盖13份、炭黑母料3.5份、抗氧剂0.4份和氧化钙0.3份,炭黑母料浓度为46%、抗氧剂1076及抗氧剂168各0.2份。
再生聚乙烯护套料密度0.945gg/cm3,熔体质量流动速率(2.16kg)0.55g/10min;再生聚乙烯棚膜料密度0.921g/10min,熔体质量流动速率((2.16kg)1.1g/10min;再生聚乙烯地膜密度为0.924g/cm3,熔体质量流动速率(2.16kg)2.4g/10min,灰分1.1%。再生防雾滴棚膜中EVA相对含量76%,LLDPE相对含量24%,灰分0.6%。再生聚乙烯瓶盖,密度为0.950g/cm3,熔体质量流动速率(2.16kg)3.2g/10min,灰分0.8%。
制备方法与实施例1相比,不同之处在于步骤(3)以及步骤(4):
步骤(3)中造粒最高温度为180℃;
(4)改性专用料制备
将上述重量份数的再生聚乙烯功能母料加入到再生聚乙烯护套料和再生聚乙烯棚膜料中经高速混合机混匀,在30℃下以转速1300转/分搅拌4min后,制得改性再生聚乙烯护套料。
将由实施例1-4制得的再生聚乙烯护套料进行性能测试,氧化诱导时间(OIT)按GB/T 19466.6-2009进行测试,采用铝杯;拉伸屈服应力及断裂伸长率按GB/T 1040.2-2006进行,压制试样,拉伸速度为50mm/min;耐环境应力开裂(ESCR)按照GB/T1842-2008进行测试,样品厚度为2mm。测试结果见表1:
表1改性再生聚乙烯护套料的物理性能
注:加工速度是在所产电缆护套为HYA 10X2X0.4型号时测试的速度。
由表1可见改性再生聚乙烯护套料的各个性能均大大提高,特别是对于护套料使用时的ESCR性能和加工时的加工速度提高显著,ESCR(10%,F0)>400,加工速度≥40m/min,耐环境应力开裂(ESCR)是对聚乙烯护套料的一个非常重要的性能要求,它直接影响到电、光缆的使用寿命,当光缆或电缆在入孔中弯曲时,聚乙烯护套就存在应力,加上长期与极性液体接触,表面便发生开裂,因此要求其具有优异的ESCR性能;另外,护套的加工速度要求较高,以满足高速生产的需要,降低生产成本。
以上所述的仅是本发明的一些实施方式。对于本领域的普通技术人员来说,在不脱离本发明创造构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。
Claims (9)
1.一种改性再生聚乙烯护套料,其特征在于,包括下列重量份的组分:再生聚乙烯护套料80-90份,再生聚乙烯功能母料10-20份,再生聚乙烯棚膜料10-15份;所述再生聚乙烯护套料密度0.943-0.953g/cm3,熔体质量流动速率(2.16kg)0.1-0.6g/10min;所述再生聚乙烯棚膜料密度0.918-0.923g/cm3,熔体质量流动速率(2.16kg)0.9-1.1g/10min。
2.根据权利要求1所述的改性再生聚乙烯护套料,其特征在于,所述再生聚乙烯功能母料由下列重量份的组分制成:再生聚乙烯地膜60-70份;再生防雾滴棚膜20-30份;再生聚乙烯瓶盖10-30份;炭黑母料3-4份;抗氧剂0.3-0.5份;消泡剂0.2-0.6份。
3.根据权利要求2所述的改性再生聚乙烯护套料,其特征在于,
所述的再生聚乙烯地膜密度为0.917~0.925g/cm3,熔体质量流动速率(2.16kg)为2.3~2.8g/10min,灰分<2%;
所述的再生防雾滴棚膜主要成分包括相对含量75%~85%的EVA和相对含量15~25%的LLDPE,灰分<2%;
所述的再生聚乙烯瓶盖密度为0.950~0.960g/cm3,熔体质量流动速率(2.16kg)为3~4g/10min,灰分<2%。
4.根据权利要求2所述的改性再生聚乙烯护套料,其特征在于,所述的抗氧剂为受阻酚类抗氧剂和亚磷酸酯类抗氧剂的复配物,两者的重量比为1:1,所述受阻酚类抗氧剂为四[β-(3,5二叔丁基-4-羟基苯基)丙酸]季戊四醇酯或β(3,5二叔丁基-4-羟基苯基)丙酸十八醇酯;所述亚磷酸酯类抗氧剂为三(2,4-二叔丁基苯基)亚磷酸酯或双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯。
5.根据权利要求2所述的改性再生聚乙烯护套料,其特征在于,所述抗氧剂为抗氧剂1076和抗氧剂168的混合物,所述炭黑母料中炭黑浓度为45-50%。
6.根据权利要求2所述的改性再生聚乙烯护套料,其特征在于,所述的消泡剂为氧化钙。
7.根据权利要求1~6任一项权利要求书所述的改性再生聚乙烯护套料的制备方法,其特征在于,由以下步骤制成:
(1)再生塑料预处理
按比例称取再生聚乙烯地膜、再生防雾滴棚膜和再生聚乙烯瓶盖,并将三种再生塑料经清洗、分离、干燥和粉碎后加入高速混合机;
(2)原料混合
按比例将炭黑母料、抗氧剂和消泡剂加入步骤(1)中的混合物中进行搅拌混合,混合条件为:搅拌转速为2000-2500转/分,搅拌时间6-10min,搅拌温度50-60℃;
(3)母料造粒
将步骤(2)中混合均匀的物料加入到双螺杆挤出机中熔融、塑化、挤出和造粒。
(4)改性专用料制备
将10-20份功能母料加入到再生聚乙烯护套料和再生聚乙烯棚膜料中,经高速混合机混匀后制得改性再生聚乙烯护套料。
8.根据权利要求7所述的改性再生聚乙烯护套料的制备方法,
其特征在于:
所述步骤(2)中抗氧剂混合前先经60℃的甲醇或者乙醇溶解;
所述步骤(3)中双螺杆挤出机的螺杆长径比为30~33;螺杆组合中有0-3段剪切块,其中包含0-1段反向剪切块;造粒温度为175-190℃;
所述步骤(4)中搅拌转速为1500-2000转/分,搅拌时间3-5min,搅拌温度30-40℃。
9.根据权利要求8所述的改性再生聚乙烯护套料的制备方法,其特征在于:所述步骤(3)中双螺杆挤出机的螺杆长径比为33;螺杆组合中有1段剪切块;造粒温度为180℃。
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