CN103554636B - 一种性能优异的电缆绝缘用材料的制备工艺 - Google Patents

一种性能优异的电缆绝缘用材料的制备工艺 Download PDF

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CN103554636B
CN103554636B CN201310508210.7A CN201310508210A CN103554636B CN 103554636 B CN103554636 B CN 103554636B CN 201310508210 A CN201310508210 A CN 201310508210A CN 103554636 B CN103554636 B CN 103554636B
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mineral filler
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杨雪洪
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SUZHOU DOUBLE-XIN NEW MATERIAL TECHNOLOGY Co Ltd
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Abstract

本发明提供一种性能优异的电缆绝缘用材料的制备工艺,其特征在于具有如下组成:以重量份计,基料100份,无机填料一20-30份,无机填料二5-10份,炭黑0.5-1.5份,硅烷偶联剂3-5份,抗氧化剂3-5份,交联剂1-3份,交联助剂0.2-0.5份,剥离剂0-2份。将上述配方通过混炼、挤出造粒、交联等适宜的加工工艺,制备得到了具有阻燃阻水同时具有优异稳定的热、力学性能的新型电缆绝缘用材料。

Description

一种性能优异的电缆绝缘用材料的制备工艺
技术领域
[0001] 本发明涉及复合材料技术领域,特别是提供一种性能优异的电缆绝缘用材料的制 备工艺。
背景技术
[0002] 电线电缆行业是电力和通信两大国民经济支柱产业的重要配套行业,在国民经济 中有着极其重要的地位,其中行业生产总量占全国总⑶P的4%。至5%。,电线电缆产品起着 输送能源、传递信息的重要作用,是国民经济的"血管"和"神经"。
[0003] 电线电缆通常是在导体芯线外包覆绝缘层构成,而聚氯乙烯以其工艺制造简单、 性能稳定,敷设方便,不受高低落差的限制等优点一直被广泛应用于电线电缆的绝缘材料, 但随着人们环保意识地不断增强,对于材料中卤素含量的限制日益严苛,加之聚氯乙烯电 线电缆固有的介质损耗大、工作温度低、耐压等级不够高等诸多缺点,其渐渐被新兴的、性 能更为优异的交联聚烯烃材料所取代。
[0004] 然而作为不含卤素的交联聚烯烃材料,为满足电缆绝缘层阻燃性能的需要,往往 要在聚烯烃中添加氢氧化镁、氢氧化铝等金属氢氧化物,但一方面添加金属氢氧化物产生 的阻燃效果较小,往往得不到所要求的阻燃性,另一方面,伴随为提高阻燃性能不不断增加 的金属氢氧化物的添加量,交联聚烯烃材料的延伸率、抗拉强度等机械性能以及耐热性能 等都会显著地降低。
[0005] 不仅如此,交联聚烯烃的局限性还在于由于其体系中交联剂分解残渣等杂质、微 孔或不均匀等缺陷存在,其在水或强电场的作用下往往会产生灌木状缺陷,也即所谓水树 影响,从而导致击穿强度降低,并最终导致电气故障。
[0006] 因此,开发一种具有优异的阻燃阻水同时具有优异稳定的热、力学性能的新型电 缆绝缘用交联聚烯烃材料,具有重要的研究意义和广泛的应用前景。
发明内容
[0007] 本发明的目的即在于提供一种具有优异的阻燃阻水同时具有优异稳定的热、力学 性能的新型电缆绝缘用交联聚烯烃材料配方及其制备工艺。
[0008] 本发明中的电缆绝缘用交联聚烯烃材料的配方如下:以重量份计,基料100份,无 机填料一 20-30份,无机填料二5-10份,炭黑0. 5-1. 5份,硅烷偶联剂3-5份,抗氧化剂3-5 份,交联剂1-3份,交联助剂0. 2-0. 5份,剥离剂0-2份。
[0009] 按所述的各组分配比进行配料并将各原料均烘干至100°C备用;然后按聚丙烯、 乙稀-乙酸乙稀酯、聚乙稀、炭黑、无机填料一、无机填料二、硅烷偶联剂、抗氧化剂、剥离剂 的顺序将各个原料先后加入密炼机进行熔融混炼,混炼的温度为200-220°C,混炼时间为 15-20min;混炼出料后经过双螺杆挤出机挤出造粒,所述螺杆直径为32mm,长径比为42 ; 造粒后进入高速捏合机喷洒交联剂及交联助剂高速混合,并控制温度在140-160°C,混合 10-15min后冷却得到产品。
[0010] 其中,所述的基料由聚乙烯、聚丙烯和乙烯-乙酸乙烯酯共聚物混合而成,其中乙 烯-乙酸乙烯酯共聚物的重量百分比为50-55%,聚丙烯的重量百分比为15-20%,所述乙 烯-乙酸乙烯酯共聚物中乙酸乙烯酯的含量为45-50% ;
[0011] 所述的无机填料一为烧结高岭土,平均粒径为1-2ym;
[0012] 所述的无机填料二为四针状氧化锌晶须,晶须平均长5-10ym;
[0013] 所述的炭黑的含碳量至少为98%,平均粒径为50-100nm,且最大粒径小于250nm, DBP为 100-150cc/100g;
[0014] 所述的硅烷偶联剂为乙烯基三_甲氧基乙氧基)硅烷;
[0015] 所述的抗氧化剂为四-[3_(3,5_二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和聚 二(2-甲基-4-羟基-5-叔丁基苯)硫醚,二者的质量比为1:1 ;
[0016] 所述的交联剂为过氧化二异丙苯;
[0017] 所述的交联助剂为三烯丙基异氰脲酸酯;
[0018] 所述的剥离剂为硅酮胶。
[0019] 本发明合理地设计了电缆绝缘用交联聚烯烃材料的配方,通过各个组分的协调作 用以及最为合适的含量配比,辅之以合理的制备工艺,获得了具有阻燃阻水同时具有优异 稳定的热、力学性能的新型电缆绝缘用材料。
具体实施方式 [0020] 实施例1.
[0021] 按表1所给出的各组分配比(其中基料满足总和为100重量份)进行配料并将各原 料均烘干至100°C备用;然后按聚丙烯(A)、乙烯-乙酸乙烯酯(B)、聚乙烯、炭黑(C)、无机 填料一(D)、无机填料二(E)、硅烷偶联剂(F)、抗氧化剂(G)、剥离剂(H)的顺序将各个原料 先后加入密炼机进行熔融混炼,混炼的温度为200-220°C,混炼时间为15-20min;混炼出料 后经过双螺杆挤出机挤出造粒,所述螺杆直径为32_,长径比为42 ;造粒后进入高速捏合 机喷洒交联剂(I)及交联助剂(J)高速混合,并控制温度在140-160°C,混合10_15min后冷 却得到产品。其中所述乙烯-乙酸乙烯酯共聚物中乙酸乙烯酯的含量为48%。
[0022] 实施例2-3以及比较例1#_9#处配方如表1所示外,制备方法均与实施例1相同。
[0023]表1
[0024]
Figure CN103554636BD00051
[0025] 各实施例的性能参数测试列于表2中,其中体积电阻率是分别在23°C和90°C两个 温度下测量的,剥离力分别在25°C和50°C两个温度下测量的。由表2的结果可知:
[0026] 聚丙烯在体系中一方面弥补乙烯-乙酸乙烯酯共聚物所导致的柔软性、耐热性变 差的问题,另一方面也同时起到耐损伤、加热变形的作用,为发挥上述功用,聚丙烯在基料 中的比例至少应达到15% ;但过多的聚丙烯添加量如超过20%则会导致体系流动性和交联 性的不足,同时也会降低体系的柔软性、伸长率、耐热老化性等等。
[0027] 乙烯-乙酸乙烯酯共聚物在体系中能够很好地发挥阻燃作用,为了达到所需的阻 燃要求,乙烯-乙酸乙烯酯在基料中的含量应达到50%,但过多的添加会导致体系的柔软 性、强度和耐热性都严重不足。乙烯-乙酸乙烯酯共聚物中乙酸乙烯酯的含量范围应在 45-50%之间,过少的含量会导致即便添加了足量的乙烯-乙酸乙烯酯共聚物仍然难以满足 阻燃需要,但过多的含量则会导致与基料其他组分的亲和性太差而影响体系的交联性以及 后续的力学性能。
[0028] 烧结高岭土无机填料对于材料的阻燃和阻水性能都有重要影响,选用经过烧结的 高岭土,其阻水性能尤其优异,同时无机填料的添加也很大程度上起到了提高强度的作用, 为了达到该无机填料的添加作用,其添加量至少应为20重量份,但过多的添加量如超过 30%则会导致体系的流动性变差,从而引起材料抗拉强度、加热老化性、柔软性等各项性能 的恶化,同时阻水性能也有所下降。需要注意的是烧结高岭土最好和本发明体系中的硅烷 偶联剂协同使用,这样能够有效提高其分散性,从而强化其使用效果。烧结高岭土的粒径为 1-2ym具有较好的分散性,以及好的强化效果。
[0029] 四针状氧化锌晶须无机填料除了能够起到提高强度的作用,主要还在其能够与抗 氧化剂发生协同的阻燃效果,能够在不添加大量金属氢氧化物阻燃剂的情况下同样具有优 异的阻燃性能,此外其还具有提高体系热稳定性的作用,为发挥其效用,其添加量至少应达 到5重量份,但过多的添加则可能导致抗拉强度等性能的下降。四针状氧化锌晶须的晶须 平均长5-10ym,这有利于其发挥提高强度的作用。
[0030] 炭黑的作用主要在于其能够有效抑制在水或强电场的作用下出现的空间电荷,从 而有效解决材料电性能的急剧破坏,为发挥上述作用,炭黑的添加量至少应达到〇. 5重量 份,但过多的添加则显然不利于绝缘材料整体电学性能的需要。炭黑的含碳量应至少达到 98%,否则会因为含有较多0 2、H2、灰分等杂质,而成为导致空间电荷出现的缺陷源,反而不利 于材料性能的改善。为发挥更好的效果,炭黑的粒径以及DBP满足平均粒径为50-100nm,且 最大粒径小于250nm,DBP为100-150cc/100g更为合适。
[0031] 硅烷偶联剂乙烯基三(P-甲氧基乙氧基)硅烷在体系中起到了明显的分散无机 填料和阻水效果,为发挥上述效果,硅烷偶联剂应至少添加3重量份,但其过量的添加会使 得材料的延伸率和耐热老化性能下降,因此其含量不应超过5重量份。
[0032] 抗氧化剂四-[3_(3, 5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和聚二(2-甲 基-4-羟基-5-叔丁基苯)硫醚为1:1的选用主要考虑到其能够与四针状氧化锌晶须发挥 很好地协同阻燃作用,以及一定的防止挤出预交联的效果,为了发挥该作用,其含量至少应 为3重量份,当超过5重量份时,阻燃效果没有显著的提高,同时可能会严重抑制后续的交 联。
[0033] 交联剂对于交联聚烯烃的添加显然是重要的,但正如已知的,其分解残渣会成为 空间电荷产生的缺陷源,因此其含量不宜过高,但为了保证体系的交联,本发明体系中添加 了必要的交联助剂三烯丙基异氰脲酸酯,从而能够合理解决上述问题。
[0034] 为了提高绝缘层与内、外屏蔽层等的剥离性能,可以在体系中加入一定量的硅酮 胶作用剥离剂,但其含量不能超过2%,否则会降低材料的成形性、力学性能。
[0035] 表 2
[0036]
Figure CN103554636BD00071
[0037]*I、浸水的条件是50°CX100日;II、加热老化的条件是125°CX7日
[0038] 对于本发明的配方体系,尽量按照聚丙烯、乙烯_乙酸乙烯酯、聚乙烯、炭黑、无机 填料一、无机填料二、硅烷偶联剂、抗氧化剂、剥离剂的顺序将各个原料先后加入密炼机进 行熔融混炼,以使得混炼更为均匀,为保证混炼充分,混炼的温度为200-220°C,混炼时间为 15-20min;混炼出料后经过双螺杆挤出机挤出造粒,所述螺杆直径为32mm,长径比为42,以 保证材料的挤出效果;造粒后进入高速捏合机喷洒交联剂(I)及交联助剂(J)高速混合,并 控制温度在140_160°C,混合10_15min后冷却得到产品,以保证材料交联度。经本发明设计 的配方,辅之以所述的制备工艺参数,即可获得具有阻燃阻水同时具有优异稳定的热、力学 性能的新型电缆绝缘用材料。

Claims (2)

1. 一种性能优异的电缆绝缘用材料的制备工艺,其特征在于:所述电缆绝缘用材料 具有如下组成,以重量份计,基料100份,无机填料一 25-30份,无机填料二7-10份,炭黑 0. 5-1. 5份,硅烷偶联剂3-5份,抗氧化剂3-5份,交联剂1-3份,交联助剂0. 2-0. 5份,剥 离剂1-2份,按所述的各组分配比进行配料并将各原料均烘干至100°C备用;然后按聚丙 稀、乙稀-乙酸乙稀酯、聚乙稀、炭黑、无机填料一、无机填料二、硅烷偶联剂、抗氧化剂、剥 离剂的顺序将各个原料先后加入密炼机进行熔融混炼,混炼的温度为200-220°C,混炼时间 为15-20min ;混炼出料后经过双螺杆挤出机挤出造粒,所述螺杆直径为32mm,长径比为42 ; 造粒后进入高速捏合机喷洒交联剂及交联助剂高速混合,并控制温度在140-160°C,混合 10-15min后冷却得到产品; 其中,所述的基料由聚乙烯、聚丙烯和乙烯-乙酸乙烯酯共聚物混合而成,其中乙 烯-乙酸乙烯酯共聚物的重量百分比为52-55%,聚丙烯的重量百分比为15-20%,所述乙 烯-乙酸乙烯酯共聚物中乙酸乙烯酯的含量为45-50% ; 所述的无机填料一为烧结高岭土,平均粒径为1-2 y m ; 所述的无机填料二为四针状氧化锌晶须,晶须平均长5-10 y m ; 所述的炭黑的含碳量至少为98%,平均粒径为50-100nm,且最大粒径小于250nm,DBP为100-150cc/100g ; 所述的硅烷偶联剂为乙烯基二(P _甲氧基乙氧基)硅烷; 所述的抗氧化剂为四_[3_(3, 5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和聚二 (2-甲基-4-羟基-5-叔丁基苯)硫醚,二者的质量比为1:1 ; 所述的交联剂为过氧化二异丙苯; 所述的交联助剂为三烯丙基异氰脲酸酯; 所述的剥离剂为硅酮胶。
2. 根据权利要求1所述的制备工艺,其特征在于:所述的三烯丙基异氰脲酸酯为0. 4 重量份。
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