CN104861309B - 耐低温epdm电缆料及其制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 229920001971 elastomer Polymers 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- 239000007822 coupling agent Substances 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims abstract description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 10
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical group C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
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- 239000004215 Carbon black (E152) Substances 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
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- LCJHLOJKAAQLQW-UHFFFAOYSA-N acetic acid;ethane Chemical compound CC.CC(O)=O LCJHLOJKAAQLQW-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 229920001897 terpolymer Polymers 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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Abstract
本发明提供耐低温EPDM电缆料,其重量份组成为:EPDM 100份,ECO橡胶9~14份,MMA 4~5份,交联剂0.3~0.5份,EVA 8~12份,相容剂3~8份,硫化剂2.5~4.5份,共硫化剂1.5~3份,填料70~90份,偶联剂0.1~0.2份,防老剂1~2份。本发明还提供了该电缆料的制备方法。本发明提供的电缆料的耐低温性能很好。
Description
技术领域:
本发明涉及EPDM电缆料,特别是涉及耐低温EPDM电缆料及其制备方法。
背景技术:
EPDM是Ethylene-Propylene-Diene Monomer的简写,中文翻译为三元乙丙橡胶,是乙烯、丙烯和非共轭二烯烃的三元共聚物。二烯烃具有特殊的结构,在进行共聚物反应时,仅有一个活性大的双键参加反应,而剩下的另一个活性较小的双键保留在共聚物分子链上成为不饱和点,供硫化使用。EPDM的主链是饱和的,这个特性使其可以耐热、耐日光、耐臭氧。EPDM本质上是无极性的,对极性溶液和化学物具有抗性,吸水率低,具有良好的绝缘特性,因此可以用作电缆料。
例如,公开号为CN103113683A、公开日为2013.05.22、申请人为安徽华宇电缆集团有限公司的中国专利申请公开了“一种耐低温风力发电专用电缆护套及其制备方法”,其组成原料的重量份为:CPE/EPDM 95-105、乙烯-醋酸乙烯共聚物25-35、聚-4-甲基-1-戊烯20-30、硬酯酸钙12-15、半补强炭黑70-90、乙撑基双硬酯酰胺25-30、聚己酸内醋3-8、N,N‘-间苯撑双马来酰亚胺5-8、防老剂TPPD 2-3、过氧化二异丙苯2-3和硼酸锌4-6。该发明解决了聚氯乙烯绝缘电力电缆在零下40℃下地方,电缆发脆不能安装和频繁扭转问题;此外,提高了电缆柔软度,在保持电缆具有较好的柔软度的情况下,提高了电缆的强度。不过,该护套的脆化温度为零下40℃,在低于此温度的环境下其各项性能大幅下降,耐低温性能不够好。
发明内容:
本发明要解决的技术问题是提供一种耐低温EPDM电缆料,其耐低温性能很好。
为解决上述技术问题,本发明的技术方案是:
耐低温EPDM电缆料,其重量份组成为:EPDM 100份,ECO橡胶9~14份,MMA 4~5份,交联剂0.3~0.5份,EVA 8~12份,相容剂3~8份,硫化剂2.5~4.5份,共硫化剂1.5~3份,填料70~90份,偶联剂0.1~0.2份,防老剂1~2份,所述交联剂为过氧缩酮。
优选地,本发明所述相容剂为EPDM-g-MAH。
优选地,本发明所述硫化剂为DTDM。
优选地,本发明所述共硫化剂为TAIC。
优选地,本发明所述填料为滑石粉、煅烧高岭土中的至少一种。
优选地,本发明所述偶联剂为KH550。
优选地,本发明所述防老剂为防老剂MB。
本发明要解决的另一技术问题是提供上述耐低温EPDM电缆料的制备方法。
为解决上述技术问题,技术方案是:
耐低温EPDM电缆料的制备方法,其步骤如下:
(1)将EPDM、MAH、DCP加入高速捏合机混合10分钟,移至双螺杆挤出机熔融挤出,双螺杆挤出机的各段温度分别为150℃、160℃、170℃,机头温度为170℃,将挤出的粒料干燥后溶于二甲苯中,60℃下回流2小时,冷却后过滤,滤饼用乙醇洗涤3次后置于真空干燥箱中90℃下干燥3小时,得到相容剂;
(2)按配方将步骤(1)得到的相容剂以及除了硫化剂、共硫化剂之外的其他组份加入密炼机100℃下混炼12分钟后得到混炼胶,将混炼胶置于开炼机上薄通2次、摆胶2次后存放9小时,与硫化剂、共硫化剂一起加入密炼机110℃下混炼1分钟,移至开炼机薄通2次、摆胶3次,压延出片后用冷却辊冷却,得到耐低温EPDM电缆料。
由上可见,与现有技术相比,本发明具有以下有益效果:
1)EVA是乙烯-乙酸乙烯(醋酸乙烯)酯共聚物,具有很好的耐低温性能,其脆化温度低至-70℃,不过其与EPDM之间的相容性不太理想,因此本发明利用马来酸酐MAH在EPDM上进行了熔融接枝制得了相容剂EPDM-g-MAH,MAH与EVA之间的相容性较好,该相容剂可有效改善EPDM、EVA之间的相容性,加强两者之间的结合力,形成均相共混,从而降低电缆料的脆化温度,提高其耐低温性能。
2)ECO橡胶为由环氧氯丙烷和环氧乙烷共聚而成的氯醚橡胶,具有很好的耐寒性,其结构中含有柔顺性较好的醚键,ECO橡胶加入EPDM后可在EPDM分子链上引入醚键,有效提高了分子链的柔顺性,从而降低其脆化温度,不过ECO橡胶与EPDM之间的相容性不佳,因此本发明还添加了MMA以及交联剂,在共混时MMA能与EPDM发生接枝共聚反应形成接枝共聚物EPDM-g-MMA以及PMMA,而ECO橡胶与PMMA能完全相容,这样便形成了相容性非常好的共混体系,从而进一步提高电缆料的耐低温性能。
具体实施方式:
下面将结合具体实施例来详细说明本发明,在此本发明的示意性实施例以及说明用来解释本发明,但并不作为对本发明的限定。
实施例1
耐低温EPDM电缆料,其重量份组成为:EPDM 100份,ECO橡胶9份,MMA 4.5份,过氧缩酮0.5份,EVA 11份,EPDM-g-MAH 4份,DTDM 3.5份,TAIC 1.8份,滑石粉84份,KH550 0.1份,防老剂MB 1.5份。
其制备方法的步骤如下:
(1)将EPDM、MAH、DCP加入高速捏合机混合10分钟,移至双螺杆挤出机熔融挤出,双螺杆挤出机的各段温度分别为150℃、160℃、170℃,机头温度为170℃,将挤出的粒料干燥后溶于二甲苯中,60℃下回流2小时,冷却后过滤,滤饼用乙醇洗涤3次后置于真空干燥箱中90℃下干燥3小时,得到相容剂;
(2)按配方将步骤(1)得到的相容剂以及除了DTDM、TAIC之外的其他组份加入密炼机100℃下混炼12分钟后得到混炼胶,将混炼胶置于开炼机上薄通2次、摆胶2次后存放9小时,与DTDM、TAIC一起加入密炼机110℃下混炼1分钟,移至开炼机薄通2次、摆胶3次,压延出片后用冷却辊冷却,得到耐低温EPDM电缆料。
实施例2
耐低温EPDM电缆料,其重量份组成为:EPDM 100份,ECO橡胶12份,MMA 4.2份,过氧缩酮0.3份,EVA 12份,EPDM-g-MAH 3份,DTDM 4份,TAIC 2.5份,煅烧高岭土85份,KH5500.1份,防老剂MB 1.8份。
其制备方法与实施例1一样。
实施例3
耐低温EPDM电缆料,其重量份组成为:EPDM 100份,ECO橡胶11份,MMA 4.8份,过氧缩酮0.3份,EVA 9.5份,EPDM-g-MAH 7份,DTDM 2.5份,TAIC 2份,煅烧高岭土75份,KH5500.2份,防老剂MB 1.4份。
其制备方法与实施例1一样。
实施例4
耐低温EPDM电缆料,其重量份组成为:EPDM 100份,ECO橡胶13份,MMA 5份,过氧缩酮0.4份,EVA 10份,EPDM-g-MAH 5份,DTDM 3份,TAIC 1.5份,滑石粉70份,KH550 0.1份,防老剂MB 2份。
其制备方法与实施例1一样。
实施例5
耐低温EPDM电缆料,其重量份组成为:EPDM 100份,ECO橡胶10份,MMA 4.4份,过氧缩酮0.5份,EVA 8份,EPDM-g-MAH 6份,DTDM 4.5份,TAIC 3份,煅烧高岭土90份,KH550 0.2份,防老剂MB 1份。
其制备方法与实施例1一样。
实施例6
耐低温EPDM电缆料,其重量份组成为:EPDM 100份,ECO橡胶14份,MMA 4.9份,过氧缩酮0.4份,EVA 9份,EPDM-g-MAH 8份,DTDM 3.4份,TAIC 2.4份,滑石粉80份,KH550 0.2份,防老剂MB 1.6份。
其制备方法与实施例1一样。
经测试,实施例1-6制得的电缆料以及对比例的脆化温度如下表所示,其中,
对比例为公开号为CN103113683A的中国专利,
脆化温度按照GB/T2951-2008进行测试。
由上表可见,本发明制得的电缆料的脆化温度明显低于对比例,具有很好的耐低温性能。
上述实施例仅例示性说明本发明的原理及其功效,而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下,对上述实施例进行修饰或改变。因此,举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变,仍应由本发明的权利要求所涵盖。
Claims (6)
1.耐低温EPDM电缆料,其特征在于:其重量份组成为:EPDM 100份,ECO橡胶9~14份,MMA 4~5份,交联剂0.3~0.5份,EVA 8~12份,相容剂3~8份,硫化剂2.5~4.5份,共硫化剂1.5~3份,填料70~90份,偶联剂0.1~0.2份,防老剂1~2份,所述交联剂为过氧缩酮;所述相容剂为EPDM-g-MAH。
2.根据权利要求1所述的耐低温EPDM电缆料,其特征在于:所述硫化剂为DTDM。
3.根据权利要求1所述的耐低温EPDM电缆料,其特征在于:所述共硫化剂为TAIC。
4.根据权利要求1所述的耐低温EPDM电缆料,其特征在于:所述填料为滑石粉、煅烧高岭土中的至少一种。
5.根据权利要求1所述的耐低温EPDM电缆料,其特征在于:所述偶联剂为KH550。
6.根据权利要求1所述的耐低温EPDM电缆料,其特征在于:所述防老剂为防老剂MB。
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