CN107236166B - 用于石油平台的低烟无卤辐照交联耐泥浆阻燃电缆料的制备工艺 - Google Patents
用于石油平台的低烟无卤辐照交联耐泥浆阻燃电缆料的制备工艺 Download PDFInfo
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Abstract
本发明一种用于低烟无毒耐热电缆材料的制备工艺,包括以下步骤:将按配方重量计量的乙烯醋酸乙烯共聚物EVA、乙烯‑醋酸乙烯‑一氧化碳三元共聚物、聚乙烯和聚乙烯接枝马来酸酐的共聚物在高速混合机中高速混合30秒钟,然后经双螺杆造粒机混合塑化造粒;将上述材料再加入按配方重量计量的炭黑、氢氧化铝阻燃剂、氢氧化镁阻燃剂、硅烷偶联剂、交联敏化剂三甲代烯丙基异氰酸酯TMAIC预聚物、抗氧剂1010、抗氧剂DLTP、硅酮母粒和润滑剂,在高速混合机中混合30秒钟,再在双阶机中捏合塑化造粒。本发明制备工艺不仅消除了高VA含量EVM在生产过程中存在发粘、结块等缺点,保持了令人满意的耐热性和低温性能,也大大降低了辐照的加工难度与加工成本。
Description
技术领域
本发明涉及低烟无卤阻燃电缆料领域,尤其涉及一种用于石油平台的低烟无卤辐照交联耐泥浆阻燃电缆料的制备工艺。
背景技术
我国海洋石油资源丰富,南海已探明的石油地质储量为230亿吨,被称为中国的波斯湾,但该地区海域较深,深水平台制造核心技术又被国外垄断,严重制约了我国南海的石油开发利用。随着2012年中国首座自主设计、建造的“第六代深水半潜式钻井平台”海洋石油981的正式开钻,标志着中国海洋石油工业的深水战略迈出了实质性的步伐,国内建造大型深水平台的技术已成熟,同时对与之配套的石油平台用用电缆也提出了更高的技术要求。
石油平台用的特种电缆,因其使用环境的特殊性,要求其具有耐油、耐泥浆、耐高温、耐低温、耐磨、高机械强度、无卤、低烟等性能。对于石油平台用电缆,更苛刻的耐油要求和耐油泥要求一直是电缆行业研究的主要难题。
目前国内不仅生产石油平台用特种电缆的厂家少,而且具备耐泥浆护套材料生产能力的厂家更是少之又少,并且在耐泥浆性能方面很不稳定,所以电缆和材料主要依赖于进口。
国内公开的有关石油平台用耐泥浆电缆专利,大多只提出护套采用的是低烟无卤耐泥浆材料,并没有指出材料的制备技术。
公开的耐泥浆电缆材料专利中,申请号为201310013029.9的专利公开了一种石油平台用电力电缆料及其制备方法,采用氢化丁腈为基体树脂,具备耐磨、抗撕、耐油、耐臭氧、耐油泥、高阻燃等性能,并满足挪威标准NEK606耐泥浆要求,但其存在成本高、燃烧时发烟量大的问题,而不利于推广应用。
申请号为201110359891.6的专利公开了一种海上平台用电缆护套材料及其制备方法,以乙烯-醋酸乙烯酯橡胶EVM为基材,与耐油性更优异的丙烯酸酯橡胶(ACM)、氢化丁腈橡胶(HNBR)、氟橡胶(FKM)共混,采用过氧化物交联体系进行硫化,具有良好的力学性能、阻燃性能、耐油泥性能,同样存在成本高、燃烧时发烟量大的问题,而且采用过氧化物交联体系进行硫化,需要专用挤出设备和庞大的专用交联管道,设备投入大,工艺繁琐,成本高。
发明内容
本发明的目的是提供一种用于石油平台的低烟无卤辐照交联耐泥浆阻燃电缆料的制备工艺,该低烟无卤辐照交联耐泥浆阻燃电缆料低烟无毒、委托辐照加工简便、投入成本低,并且可以生产满足挪威NEK606海上平台用无卤/防泥浆电缆标准的无卤阻燃耐泥浆护套料;同时提供一种用于上述石油平台用辐照交联耐泥浆低烟无卤阻燃电缆料的制备方法。
为达到上述发明目的,本发明采用的辐照交联耐泥浆无卤阻燃电缆料的技术方案是:一种用于石油平台的低烟无卤辐照交联耐泥浆阻燃电缆料的制备工艺,原料配方由下列重量份的材料组成:
乙烯醋酸乙烯共聚物35份、乙烯-醋酸乙烯-一氧化碳三元共聚物15份、聚乙烯40份、聚乙烯接枝马来酸酐的共聚物10份、炭黑8.2份、氢氧化铝阻燃剂105份、氢氧化镁阻燃剂25份、硅烷偶联剂1.3份、交联敏化剂2.4份、抗氧剂1010为0.9份、抗氧剂DLTP0.9份、硅酮母粒3.5份、PE蜡0.7份;
其中,所述乙烯醋酸乙烯共聚物中的醋酸乙烯VA含量为33%,此乙烯醋酸乙烯共聚物的熔体指数为0.2g/10min;
所述乙烯-醋酸乙烯-一氧化碳三元共聚物中一氧化碳含量为8~12%,乙烯-醋酸乙烯-一氧化碳三元共聚物中的醋酸乙烯VA含量为24~30%,所述乙烯-醋酸乙烯-一氧化碳三元共聚物的熔体指数为35g/10min;
所述聚乙烯为高密度聚乙烯,熔体指数为0.08g/10min;
所述聚乙烯接枝马来酸酐的共聚物的接枝率为0.6%~1.2%;
所述炭黑为炉法生成的炭黑,粒径为12~30nm,吸油值为50~80cc/100g;
所述无卤阻燃剂为氢氧化铝和氢氧化镁按照2~3:1质量比复配形成的混合物,且其平均粒径皆为0.8~1.5μm;
所述偶联剂为硅烷偶联剂A-172或Z-6173;
所述交联敏化剂为三甲代烯丙基异氰酸酯TMAIC预聚物,分子结构如下图所示,聚合度n为2~10,其单体为三甲代烯丙基异氰酸酯TMAIC,分子量为291.35;
所述抗氧剂为1010和DLTP按照0.8~1:1~1.2的质量比复配的混合物。
上述技术方案进一步改进的技术方案如下:
1. 上述方案中,原料配方由下列重量份的材料组成:
乙烯醋酸乙烯共聚物 25~45份,
乙烯-醋酸乙烯-一氧化碳三元共聚物 12~18份,
聚乙烯 30~45份,
聚乙烯接枝马来酸酐的共聚物 5~12份,
炭黑 8~10份,
无卤阻燃剂 125~150份,
偶联剂 1~1.5份,
交联敏化剂 2~3份,
抗氧剂 1.6~2.4份,
硅酮 3~4份,
润滑剂 0.5~1份。
2. 上述方案中,原料配方由下列重量份的材料组成:
乙烯醋酸乙烯共聚物 35~40份,
乙烯-醋酸乙烯-一氧化碳三元共聚物 12~16份,
聚乙烯 30~40份,
聚乙烯接枝马来酸酐的共聚物 8~12份,
炭黑 8~9.5份,
无卤阻燃剂 135~150份,
偶联剂 1.2~1.5份,
交联敏化剂 2.4~2.8份,
抗氧剂 1.8~2.2份,
硅酮 3~3.5份,
润滑剂 0.6~0.8份。
3. 上述方案中,所述硅酮母粒中有效成分硅酮的质量含量为50%,所述润滑剂为PE蜡、EVA蜡、硬脂酸钙或硬脂酸锌中的至少一种。
为达到上述发明目的,本发明采用的石油平台用辐照交联耐泥浆无卤阻燃电缆料的制备方法,包括以下步骤:
第一步:将按配方重量计量的乙烯醋酸乙烯共聚物EVA、乙烯-醋酸乙烯-一氧化碳三元共聚物、聚乙烯和聚乙烯接枝马来酸酐的共聚物在高速混合机中高速混合30秒钟,然后经双螺杆造粒机混合塑化造粒,加工温度为:输送段120~130℃,熔融段140~155℃,混炼段160~170℃,排气段155~165℃,均化段155~165℃,机头160~170℃;
第二步:将上述材料再加入按配方重量计量的炭黑、氢氧化铝阻燃剂、氢氧化镁阻燃剂、硅烷偶联剂、交联敏化剂三甲代烯丙基异氰酸酯TMAIC预聚物、抗氧剂1010、抗氧剂DLTP、硅酮母粒和润滑剂,在高速混合机中混合30秒钟,再在双阶机中捏合塑化造粒,双阶机包括双螺杆的加工温度为:输送段100~115℃,熔融段120~135℃,混炼段140~150℃,排气段145~155℃,均化段145~155℃,机头150~160℃,包括单螺杆温度为:第一区120~135℃,第二区120~135℃,第三区120~135℃,机头130~145℃,切粒风冷后包装;
第三步:将第二步所得材料在电线电缆挤线机生产线上,在一区110~120℃,二区120~140℃,三区135~155℃,四区135~155℃,机头130~150℃的温度下挤出,包覆在导体线芯上,再进行辐照加工,辐照后热延伸15%~25%。
由于上述技术方案的运用,本发明与现有技术相比具有下列优点:
1. 本发明用于石油平台的低烟无卤辐照交联耐泥浆阻燃电缆料的制备工艺,选用乙烯醋酸乙烯共聚物EVA、乙烯-醋酸乙烯-一氧化碳三元共聚物、聚乙烯和聚乙烯接枝马来酸酐的共聚物作为基材树脂,添加氢氧化铝和氢氧化镁阻燃剂,及炉法炭黑,并在硅烷偶联剂、交联敏化剂TMAIC预聚物和抗氧剂等助剂作用下采用双阶机,即有双螺杆和单螺杆组成的设备,经两步法技术,可以提高共混材料中填料和基材的相容性,提高材料的机械性能;最终制得符合挪威NEK606海上平台用无卤/防泥浆电缆标准的耐泥浆电缆用的无卤阻燃护套材料,经辐照加工后成为石油平台用辐照交联耐泥浆低烟无卤阻燃电缆。
2. 本发明用于石油平台的低烟无卤辐照交联耐泥浆阻燃电缆料的制备工艺,基材选用乙烯-醋酸乙烯-一氧化碳三元共聚物是本发明的特点之一,该共聚物可以在保持VA含量较低的情况下,耐油性能相当于高VA含量的EVM;与EVA共聚物、高密度聚乙烯及PE接枝马来酸酐共聚物进行合理复配,不仅消除了高VA含量EVM在生产过程中存在发粘、结块等缺点,保持了令人满意的耐热性和低温性能;更重要的是,在炉法炭黑(3.3%~3.5%比例)的补强作用下,取得了优越的高耐油性能及耐泥浆性能,辐照后,通过挪威标准NEK606的耐油耐泥浆性能要求。
3. 本发明用于石油平台的低烟无卤辐照交联耐泥浆阻燃电缆料的制备工艺,采用三甲代烯丙基异氰酸酯TMAIC预聚物作为交联敏化剂,是本发明的另一大特点,将TMAIC预聚物使用到配方中后,大幅提高了产品的辐照交联效果,在相同热延伸率(10%)的要求下,辐照剂量从原来的25Mrad降低到目前的15Mrad,大大降低了辐照的加工难度与加工成本,保证其容易达到高耐油耐泥浆所需的低热延伸率的辐照交联要求,进一步促成高耐油耐泥浆方案的实现。
4. 本发明用于石油平台的低烟无卤辐照交联耐泥浆阻燃电缆料的制备工艺,使用氢氧化铝、氢氧化镁,赋予产品无卤阻燃特性,与润滑剂硅酮母粒配合使用,具有明显的协效作用,可以提高复合阻燃体系的结壳、耐滴落等阻燃效果。同时添加硅烷偶联剂对无机填料进行改性,能够提高无机阻燃剂与基料之间的相容性,这样,对于提高材料老化性能、耐油性及耐泥浆性能都是有益的。抗氧化体系采用抗氧剂1010和DLTP配合使用的方式,具有明显协同效果,使得产品在明显减少抗氧剂用量的同时,仍可满足一定的老化性能要求,即经一定的高温老化后,材料结构和性能具有一定的保持性,同时也保证了产品的耐油性和耐泥浆性能;对常规低烟无卤阻燃电缆料的配方进行技术改进,通过添加乙烯-醋酸乙烯-一氧化碳三元共聚物与炭黑补强配合,以及高效的交联敏化剂TMAIC预聚物对交联效果的促进,有效地提高了无卤阻燃护套料的耐油性能和耐泥浆性能,最终可以很好地满足挪威NEK606海上平台用无卤/防泥浆电缆标准的要求。
具体实施方式
下面结合实施例对本发明作进一步描述:
实施例:一种用于石油平台的低烟无卤辐照交联耐泥浆阻燃电缆料的制备工艺,材料配方:
2、制备工艺
第一步:将按配方重量计量的乙烯醋酸乙烯共聚物EVA、乙烯-醋酸乙烯-一氧化碳三元共聚物、聚乙烯和聚乙烯接枝马来酸酐的共聚物在高速混合机中高速混合30秒钟,然后经双螺杆造粒机混合塑化造粒,加工温度为:输送段120~130℃,熔融段140~155℃,混炼段160~170℃,排气段155~165℃,均化段155~165℃,机头160~170℃。
第二步:将上述材料再加入按配方重量计量的炭黑、氢氧化铝阻燃剂、氢氧化镁阻燃剂、硅烷偶联剂、交联敏化剂三甲代烯丙基异氰酸酯TMAIC预聚物、抗氧剂1010、抗氧剂DLTP、硅酮母粒和润滑剂,在高速混合机中混合30秒钟,再在双阶机中捏合塑化造粒,双阶机包括双螺杆的加工温度为:输送段100~115℃,熔融段120~135℃,混炼段140~150℃,排气段145~155℃,均化段145~155℃,机头150~160℃,包括单螺杆温度为:第一区120~135℃,第二区120~135℃,第三区120~135℃,机头130~145℃,切粒风冷后包装。
第三步:将第二步所得材料在电线电缆挤线机生产线上,在一区110~120℃,二区120~140℃,三区135~155℃,四区135~155℃,机头130~150℃的温度下挤出,包覆在导体线芯上,再进行辐照加工,辐照后热延伸15%~25%,即成为满足挪威NEK606海上平台用无卤/防泥浆电缆标准的电缆,按照电缆标准对各项指标进行检测。
3、技术指标
由上述实施例可以看出,本发明在材料配方中通过添加乙烯-醋酸乙烯-一氧化碳三元共聚物及高效交联敏化剂TMAIC预聚物,使得材料可以发生更充分均匀有效的交联反应,既而具有更高的耐油性和耐泥浆性能;使用该电缆护套料制得的产品可以满足挪威NEK606海上平台用无卤/防泥浆电缆标准的要求。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (2)
1.一种用于石油平台的低烟无卤辐照交联耐泥浆阻燃电缆料的制备工艺,其特征在于:原料配方由下列重量份的材料组成:乙烯醋酸乙烯共聚物35份、乙烯-醋酸乙烯-一氧化碳三元共聚物15份、聚乙烯40份、聚乙烯接枝马来酸酐的共聚物10份、炭黑8.2份、氢氧化铝阻燃剂105份、氢氧化镁阻燃剂25份、硅烷偶联剂1.3份、交联敏化剂2.4份、抗氧剂1010为0.9份、抗氧剂DLTP0.9份、硅酮母粒3.5份、PE蜡0.7份;所述聚乙烯接枝马来酸酐的共聚物的接枝率为1%;所述聚乙烯为高密度聚乙烯,熔体指数为0 .08g/10min;
所述制备工艺包括以下步骤:
第一步:将按配方重量计量的乙烯醋酸乙烯共聚物EVA、乙烯-醋酸乙烯-一氧化碳三元共聚物、聚乙烯和聚乙烯接枝马来酸酐的共聚物在高速混合机中高速混合30秒钟,然后经双螺杆造粒机混合塑化造粒,加工温度为:输送段120~130℃,熔融段140~155℃,混炼段160~170℃,排气段155~165℃,均化段155~165℃,机头160~170℃;
第二步:将上述材料再加入按配方重量计量的炭黑、氢氧化铝阻燃剂、氢氧化镁阻燃剂、硅烷偶联剂、交联敏化剂三甲代烯丙基异氰酸酯TMAIC预聚物、抗氧剂1010、抗氧剂DLTP、硅酮母粒和润滑剂,在高速混合机中混合30秒钟,再在双阶机中捏合塑化造粒,双阶机包括双螺杆的加工温度为:输送段100~115℃,熔融段120~135℃,混炼段140~150℃,排气段145~155℃,均化段145~155℃,机头150~160℃,包括单螺杆温度为:第一区120~135℃,第二区120~135℃,第三区120~135℃,机头130~145℃,切粒风冷后包装;
第三步:将第二步所得材料在电线电缆挤线机生产线上,在一区110~120℃,二区120~140℃,三区135~155℃,四区135~155℃,机头130~150℃的温度下挤出,包覆在导体线芯上,再进行辐照加工,辐照后热延伸15%~25%;
其中,所述乙烯醋酸乙烯共聚物中的醋酸乙烯VA含量为33%,此乙烯醋酸乙烯共聚物的熔体指数为0.2g/10min;
所述乙烯-醋酸乙烯-一氧化碳三元共聚物中一氧化碳含量为8~12%,乙烯醋酸乙烯共聚物EVA中的醋酸乙烯VA含量为24~30%,所述乙烯-醋酸乙烯-一氧化碳三元共聚物的熔体指数为35g/10min;
所述聚乙烯为高密度聚乙烯,熔体指数为0.08g/10min;
所述炭黑为炉法生成的炭黑,粒径为12~30nm,吸油值为50~80cc/100g;
所述硅烷偶联剂为硅烷偶联剂A-172或Z-6173;
所述交联敏化剂为三甲代烯丙基异氰酸酯TMAIC预聚物,分子结构如下图所示,聚合度n为2~10,其单体为三甲代烯丙基异氰酸酯TMAIC,分子量为291.35;
所述氢氧化铝阻燃剂,化学法并表面硅烷处理,平均粒径为 0.8-1.5 微米,重量份为105 份,所述氢氧化镁阻燃剂,化学法并表面硅烷处理,平均粒径为 0.8-1.5 微米,重量份为 25 份。
2.根据权利要求1所述的用于石油平台的低烟无卤辐照交联耐泥浆阻燃电缆料的制备工艺,其特征在于:所述氢氧化铝阻燃剂105份、氢氧化镁阻燃剂25份的平均粒径皆为0.8~1.5μm。
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CN104327367A (zh) * | 2014-10-17 | 2015-02-04 | 上海至正道化高分子材料股份有限公司 | 大截面电线电缆用低烟低卤阻燃辐照交联料 |
CN104371182A (zh) * | 2014-11-10 | 2015-02-25 | 长园集团股份有限公司 | 一种135℃辐照交联聚烯烃热缩管 |
CN104530552A (zh) * | 2015-01-22 | 2015-04-22 | 深圳市沃尔核材股份有限公司 | 一种耐高低温冲击热缩管 |
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