CN114055885B - 多层共挤电磁屏蔽氟塑料电绝缘波纹管材及其制备方法 - Google Patents
多层共挤电磁屏蔽氟塑料电绝缘波纹管材及其制备方法 Download PDFInfo
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- CN114055885B CN114055885B CN202111417795.2A CN202111417795A CN114055885B CN 114055885 B CN114055885 B CN 114055885B CN 202111417795 A CN202111417795 A CN 202111417795A CN 114055885 B CN114055885 B CN 114055885B
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- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 93
- 238000009413 insulation Methods 0.000 title claims abstract description 25
- 238000001125 extrusion Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 44
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000007493 shaping process Methods 0.000 claims abstract description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 69
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 59
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 36
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- 239000004033 plastic Substances 0.000 claims description 21
- 229920003023 plastic Polymers 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
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- 239000001257 hydrogen Substances 0.000 claims description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
- 239000011737 fluorine Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
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- 238000005507 spraying Methods 0.000 claims description 15
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 14
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
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- 238000002156 mixing Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
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- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
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- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical compound FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 claims description 3
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- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 63
- 238000005260 corrosion Methods 0.000 abstract description 3
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Abstract
本发明提供了一种多层共挤电磁屏蔽氟塑料电绝缘波纹管材及其制备方法。所述管材包括绝缘层和电磁屏蔽层,绝缘层的壁厚为0.1‑2mm,电磁屏蔽层的壁厚为0.1‑3mm。所述绝缘层为内绝缘层和/或外绝缘层,所述内绝缘层位于电磁屏蔽层的内侧,所述外绝缘层位于电磁屏蔽层的外侧。所述制备方法包括将绝缘母粒和电磁屏蔽母粒分别放入相应的挤出机中,多层共挤挤出氟塑料直管,将未完全冷却的氟塑料直管在波纹管设备模具中连续成型,循环冷水冷却定型,收卷机收卷。本发明采用多层共挤和波纹一次成型,使其具有14kHz‑30MHz、30MHz‑1GHz、1GHz‑18GHz不同频段电磁屏蔽效能的同时,具有单层电绝缘和双层电绝缘功能,还有耐低温、耐高温、耐老化、长寿命、耐盐雾、耐腐蚀、阻燃性、环柔性等特点。
Description
技术领域
本发明涉及电磁屏蔽及电缆领域,具体的涉及一种多层共挤电磁屏蔽氟塑料电绝缘波纹管材及其制备方法。
背景技术
塑料波纹管广泛用于航天、军工、石化、化工、电力冶金等行业的重要管道。如固定翼飞机、直升机、汽车、通信装备、工程装备等线束防护、整理,应用十分广泛。塑料波纹管主要有:PE波纹管、PA波纹管、PP波纹管、PVC波纹管等。它们具有一定的寿命、防水、防尘、易弯曲的特点,但也存在着不同程度的弱点和不足。如:PE波纹管不耐高温、PA波纹管可燃、PP波纹管耐候性不足,PVC环保性差等问题,这些塑料波纹管配套使用都存在不同的局限性,不能完全满足使用需求。另外,随着高端用电设备、电器应用普及,对现有波纹管的性能要求越来越高,用电设备之间、电器之间的电磁干扰越发严重,也得到了不同程度的重视和解决。但是,设备、电器通电导线及接口的电磁散射也会直接影响设备、电器的性能,目前还没有得到重视和解决,高性能电磁屏蔽塑料波纹管的需求越来越急迫。
发明内容
鉴于背景技术中存在的问题,本发明的目的在于提供一种多层共挤电磁屏蔽氟塑料电绝缘波纹管材及其制备方法,根据不同的应用需求,采用不同氟塑料与助剂科学配比,采用多层共挤和波纹一次成型,使其具有14kHz-30MHz、30MHz-1GHz、1GHz-18GHz不同频段电磁屏蔽效能的同时,具有单层电绝缘和双层电绝缘功能,还有耐低温、耐高温、耐老化、长寿命、耐盐雾、耐腐蚀、阻燃性、环柔性等特点,填补了该领域高端波纹管材的技术空白。
为了实现上述目的,在第一方面,本发明提供了一种多层共挤电磁屏蔽氟塑料电绝缘波纹管材,包括绝缘层和电磁屏蔽层,绝缘层的壁厚为0.1-2mm,电磁屏蔽层的壁厚为0.1-3mm。
可选的,绝缘层为内绝缘层和/或外绝缘层,所述内绝缘层位于电磁屏蔽层的内侧,所述外绝缘层位于电磁屏蔽层的外侧。
可选的,电磁屏蔽层包括可熔融氟塑料、电磁屏蔽材料、马来酸酐接枝可熔融含氢氟塑料和分散剂;电磁屏蔽材料为碳纤维、导电碳黑、碳纳米管、石墨烯、黄铜短纤维、镍及镀镍石墨纤维、导电银粉、导电石墨和导电金属的一种或组合;分散剂为纳米二氧化硅、聚四氟乙烯微粉蜡的一种或组合。
可选的,绝缘层包含可熔融氟塑料、辐照交联剂和马来酸酐接枝可熔融含氢氟塑料;所述辐照交联剂为异氰脲酸三烯丙酯(TAIC)、三烯丙基氰尿酸酯(TAC)中的一种或组合。
可选的,可熔融氟塑料为全氟乙烯丙烯共聚物(FEP)、四氟乙烯-全氟烷氧基乙烯基醚共聚物(PFA)、聚三氟氯乙烯(PCTFE)、乙烯-三氟氯乙烯共聚物(ECTFE)、乙烯-四氟乙烯共聚物(ETFE)和聚偏氟乙烯(PVDF)中的一种或组合。
可选的,马来酸酐接枝可熔融含氢氟塑料为马来酸酐接枝乙烯-四氟乙烯共聚物(ETFE)或马来酸酐接枝聚偏氟乙烯(PVDF);优选的可熔融氟塑料和马来酸酐接枝可熔融含氢氟塑料的组合为乙烯-四氟乙烯共聚物(ETFE)和马来酸酐接枝乙烯-四氟乙烯共聚物(ETFE),或者聚偏氟乙烯(PVDF)和马来酸酐接枝聚偏氟乙烯(PVDF)。
可选的,马来酸酐接枝可熔融含氢氟塑料的制备方法包括以下步骤:将马来酸酐溶于无水乙醇制备质量浓度30-50%的溶液;将溶液喷淋于高速搅拌机中的可熔融含氢氟塑料中,高速搅拌均匀,鼓风干燥箱中90-100℃鼓风干燥2-5h,然后在温度80-90℃下用伽马射线辐照,辐照剂量1-2Mrad,得到预接枝混合料;所述预接枝混合料用异向啮合双螺杆挤出机挤出造粒,得到马来酸酐接枝可熔融含氢氟塑料。
为了实现上述目的,在第二方面,本发明提供了一种多层共挤电磁屏蔽氟塑料电绝缘波纹管材的制备方法,包括以下步骤:将绝缘母粒和电磁屏蔽母粒分别放入相应的挤出机中,多层共挤挤出氟塑料直管,将未完全冷却的氟塑料直管在波纹管设备模具中连续成型,循环冷水冷却定型,收卷机收卷。
可选的,绝缘母粒的制备方法包括如下步骤:(1)将辐照交联剂溶于无水乙醇制备质量浓度30-50%的溶液;(2)将溶液喷淋于高速搅拌机中的可熔融氟塑料和马来酸酐接枝可熔融含氢氟塑料,高速搅拌均匀,鼓风干燥箱中100-105℃干燥2-5h,得到预混料;(3)将预混料在室温条件下用伽马射线或电子束辐照,辐照剂量3-5Mrad,得到预交联混合料;(4)所述预交联混合料用异向啮合双螺杆挤出机挤出造粒,对得到的粒料进行第二次辐照活化,辐照剂量0.5-1Mrad,得到绝缘母粒。
可选的,电磁屏蔽母粒的制备方法包括以下步骤:将可熔融氟塑料、电磁屏蔽材料、马来酸酐接枝可熔融含氢氟塑料和分散剂按配比100:(0.1-30):(10-30)(0.1-4),加入高速搅拌机中,高速搅拌为5-8分钟,搅拌温度为:40—80℃。得到预分散电磁屏蔽混合材料,所述的预分散电磁屏蔽混合料用异向啮合双螺杆挤出机挤出造粒,得到电磁屏蔽母粒。
本发明的有益效果如下:
(1)本发明采用伽马射线辐照法,伽马射线可以促进绝缘层发生均匀的交联反应,该层中的马来酸酐接枝可熔融含氢氟塑料中的马来酸酐或马来酸基团可与交联反应生成的元素氟反应,生成-COF,消耗掉元素氟,可有效控制交联反应的速率或交联度。绝缘层和电磁屏蔽层的界面处发生交联键合,避免因各层成分的差异而产生层间剥离问题,提高使用过程中的弯曲柔韧性或强度。
(2)电磁屏蔽层中马来酸酐接枝可熔融氟塑料的马来酸酐或马来酸基团,可与电磁屏蔽材料,如导电碳黑表面的羟基发生反应,一方面提高电磁屏蔽材料的相容性和分散性,进而改善电磁屏蔽材料的增强和电磁屏蔽作用,同等条件下会改善柔韧性。
(3)喷洒到可熔融氟塑料原料表面的辐照交联剂与可熔融氟塑料接枝交联,防止辐照交联剂在后续高温造粒过程中的挥发;造粒后的第二次辐照交联同样提高辐照交联剂的交联度,特定的辐照剂量可有效控制母粒的交联度,不影响后续加工,并极大提升绝缘层的交联度。
(4)本发明的可熔融氟塑料管材制备方法兼顾生产工艺简单,成本低,易于实现,同时得到的管材性能在耐高低温性、机械强度、柔韧性、耐腐蚀、耐渗透性和电磁屏蔽等方面优于其他非氟塑料管材,电磁屏蔽效能突出。
附图说明
图1为根据本发明实施例1制备的多层共挤电磁屏蔽氟塑料电绝缘波纹管材的截面图。
图2为根据本发明实施例2制备的多层共挤电磁屏蔽氟塑料电绝缘波纹管材的截面图。
图3为根据本发明实施例3制备的多层共挤电磁屏蔽氟塑料电绝缘波纹管材的截面图。
附图标记
1-内绝缘层,2-电磁屏蔽层,3-外绝缘层。
具体实施方式
为使发明的上述目的、特征和优点能够更加明显易懂,下面对本发明的具体实施方式做详细的说明。
在下面的描述中阐述了很多具体细节以便于充分理解本发明,但是本发明还可以采用其他不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似推广,因此本发明不受下面公开的具体实施例的限制。
首先,说明根据本发明第一方面提供了一种多层共挤电磁屏蔽氟塑料电绝缘波纹管材,包括绝缘层和电磁屏蔽层,绝缘层的壁厚为0.1-2mm,电磁屏蔽层的壁厚为0.1-3mm。
在根据本发明的一实施例中,绝缘层为内绝缘层和/或外绝缘层,所述内绝缘层位于电磁屏蔽层的内侧,所述外绝缘层位于电磁屏蔽层的外侧。
在根据本发明的一实施例中,电磁屏蔽层包括可熔融氟塑料、电磁屏蔽材料、马来酸酐接枝可熔融含氢氟塑料和分散剂;电磁屏蔽材料为碳纤维、导电碳黑、碳纳米管、石墨烯、黄铜短纤维、镍及镀镍石墨纤维、导电银粉、导电石墨和导电金属的一种或组合;分散剂为纳米二氧化硅、聚四氟乙烯微粉蜡的一种或组合。
在根据本发明的一实施例中,绝缘层包含可熔融氟塑料、辐照交联剂和马来酸酐接枝可熔融含氢氟塑料;所述辐照交联剂为异氰脲酸三烯丙酯(TAIC)、三烯丙基氰尿酸酯(TAC)中的一种或组合。
在根据本发明的一实施例中,可熔融氟塑料为全氟乙烯丙烯共聚物(FEP)、四氟乙烯-全氟烷氧基乙烯基醚共聚物(PFA)、聚三氟氯乙烯(PCTFE)、乙烯-三氟氯乙烯共聚物(ECTFE)、乙烯-四氟乙烯共聚物(ETFE)和聚偏氟乙烯(PVDF)中的一种或组合。
在根据本发明的一实施例中,马来酸酐接枝可熔融含氢氟塑料为马来酸酐接枝乙烯-四氟乙烯共聚物(ETFE)或马来酸酐接枝聚偏氟乙烯(PVDF);优选的是可熔融氟塑料和马来酸酐接枝可熔融含氢氟塑料的组合为乙烯-四氟乙烯共聚物(ETFE)和马来酸酐接枝乙烯-四氟乙烯共聚物(ETFE),或者聚偏氟乙烯(PVDF)和马来酸酐接枝聚偏氟乙烯(PVDF)。
在根据本发明的一实施例中,马来酸酐接枝可熔融含氢氟塑料的制备方法包括以下步骤:将马来酸酐溶于无水乙醇制备质量浓度30-50%的溶液;将溶液喷淋于高速搅拌机中的可熔融含氢氟塑料中,高速搅拌均匀,鼓风干燥箱中90-100℃鼓风干燥2-5h,然后在温度80-90℃下用伽马射线辐照,辐照剂量1-2Mrad,得到预接枝混合料;所述预接枝混合料用异向啮合双螺杆挤出机挤出造粒,得到马来酸酐接枝可熔融含氢氟塑料。
其次,说明根据本发明第二方面的多层共挤电磁屏蔽氟塑料电绝缘波纹管材的制备方法,包括以下步骤:将绝缘母粒和电磁屏蔽母粒分别放入相应的挤出机中,多层共挤挤出氟塑料直管,将未完全冷却的氟塑料直管在波纹管设备模具中连续成型,循环冷水冷却定型,收卷机收卷。
在根据本发明的一实施例中,绝缘母粒的制备方法包括如下步骤:(1)将辐照交联剂溶于无水乙醇制备质量浓度30-50%的溶液;(2)将溶液喷淋于高速搅拌机中的可熔融氟塑料和马来酸酐接枝可熔融含氢氟塑料,高速搅拌均匀,鼓风干燥箱中100-105℃干燥2-5h,得到预混料;(3)将预混料在室温条件下用伽马射线或电子束辐照,辐照剂量3-5Mrad,得到预交联混合料;(4)所述预交联混合料用异向啮合双螺杆挤出机挤出造粒,对得到的粒料进行第二次辐照活化,辐照剂量0.5-1Mrad,得到绝缘母粒。
在根据本发明的一实施例中,电磁屏蔽母粒的制备方法包括以下步骤:将可熔融氟塑料、电磁屏蔽材料、马来酸酐接枝可熔融含氢氟塑料和分散剂按配比100:(0.1-30):(10-30):(0.1-4),加入高速搅拌机中,高速搅拌为5-8分钟,搅拌温度为40—80℃,得到预分散电磁屏蔽混合材料,所述的预分散电磁屏蔽混合料用异向啮合双螺杆挤出机挤出造粒,得到电磁屏蔽母粒。
接下来参照附图对本发明的制备方法进行说明。
首先,制备马来酸酐接枝可熔融含氢氟塑料:将马来酸酐溶于无水乙醇制备质量浓度30-50%的溶液;将溶液喷淋于高速搅拌机中的可熔融含氢氟塑料中,高速搅拌均匀,鼓风干燥箱中90-100℃鼓风干燥2-5h,然后在温度80-90℃下用伽马射线辐照,辐照剂量1-2Mrad,得到预接枝混合料;所述预接枝混合料用异向啮合双螺杆挤出机挤出造粒,得到马来酸酐接枝可熔融含氢氟塑料。
其次,制备绝缘母粒:(1)将辐照交联剂溶于无水乙醇制备质量浓度30-50%的溶液;(2)将溶液喷淋于高速搅拌机中的可熔融氟塑料和马来酸酐接枝可熔融含氢氟塑料,高速搅拌均匀,鼓风干燥箱中100-105℃干燥2-5h,得到预混料;(3)将预混料在室温条件下用伽马射线或电子束辐照,辐照剂量3-5Mrad,得到预交联混合料;(4)所述预交联混合料用异向啮合双螺杆挤出机挤出造粒,对得到的粒料进行第二次辐照活化,辐照剂量0.5-1Mrad,得到绝缘母粒。
再者,制备电磁屏蔽母粒:将可熔融氟塑料、电磁屏蔽材料、马来酸酐接枝可熔融含氢氟塑料和分散剂按配比100:(0.1-30):(10-30):(0.1-4),加入高速搅拌机中,高速搅拌为5-8分钟,搅拌温度为40—80℃,得到预分散电磁屏蔽混合材料,所述的预分散电磁屏蔽混合料用异向啮合双螺杆挤出机挤出造粒,得到电磁屏蔽母粒。
最后,制备多层共挤电磁屏蔽氟塑料电绝缘波纹管材:将绝缘母粒和电磁屏蔽母粒分别放入相应的挤出机中,多层共挤挤出氟塑料直管,将未完全冷却的氟塑料直管在波纹管设备模具中连续成型,循环冷水冷却定型,收卷机收卷。
以下结合具体实例对本发明的多层共挤电磁屏蔽氟塑料电绝缘波纹管材及其制备方法做具体说明。
所用主要原材料及设备:原材料和设备为市售;
PVDF:浙江巨化化工材料有限公司;
ETFE:牌号DS405,山东东岳含氟功能膜材料国家重点实验室;
辐照交联剂:异氰脲酸三烯丙酯(TAIC),三烯丙基氰尿酸酯(TAC),市售;
电磁屏蔽材料:市售;
马来酸酐:济南金昊化工有限公司;
伽马射线源:Co-60。
实施例1
首先,制备马来酸酐接枝乙烯-四氟乙烯(ETFE)共聚物:将马来酸酐溶于无水乙醇制备质量浓度30%的溶液;将溶液喷淋于高速搅拌机中的乙烯-四氟乙烯共聚物(ETFE)中,高速搅拌均匀,鼓风干燥箱中90℃鼓风干燥2h,然后在温度80℃下用伽马射线辐照,辐照剂量1Mrad,得到预接枝混合料;所述预接枝混合料用异向啮合双螺杆挤出机挤出造粒,得到马来酸酐接枝乙烯-四氟乙烯共聚物(ETFE)。
其次,制备绝缘母粒:(1)将异氰脲酸三烯丙酯(TAIC)溶于无水乙醇制备质量浓度30%的溶液;(2)将溶液喷淋于高速搅拌机中的乙烯-四氟乙烯共聚物(ETFE)和马来酸酐接枝乙烯-四氟乙烯共聚物(ETFE),高速搅拌均匀,鼓风干燥箱中100℃干燥2h,得到预混料;其中异氰脲酸三烯丙酯(TAIC)、乙烯-四氟乙烯共聚物(ETFE)和马来酸酐接枝乙烯-四氟乙烯共聚物(ETFE)的质量比为0.5:100:10;(3)将预混料在室温条件下用Co-60伽马射线源辐照,辐照剂量3Mrad,得到预交联混合料;(4)所述预交联混合料用异向啮合双螺杆挤出机挤出造粒,对得到的粒料进行第二次辐照活化,辐照剂量0.5Mrad,得到绝缘母粒。
再者,制备电磁屏蔽母粒:将乙烯-四氟乙烯共聚物(ETFE)、导电碳黑、马来酸酐接枝乙烯-四氟乙烯共聚物(ETFE)和纳米二氧化硅按质量配比100:10:10:0.1,加入高速搅拌机中,高速搅拌为5分钟,搅拌温度40℃,得到预分散电磁屏蔽混合材料,所述预分散电磁屏蔽混合料用异向啮合双螺杆挤出机挤出造粒,得到电磁屏蔽母粒。
最后,制备三层共挤电磁屏蔽氟塑料电绝缘波纹管材:将内绝缘层的绝缘母粒、电磁屏蔽母粒和外绝缘层的绝缘母粒、按出料质量比例1:1:1分别放入相应的挤出机中,三层共挤挤出氟塑料直管,将未完全冷却的氟塑料直管在波纹管设备模具中连续成型,循环冷水冷却定型,收卷机收卷,得到图1所示的管材。
实施例2
首先,马来酸酐接枝聚偏氟乙烯(PVDF):将马来酸酐溶于无水乙醇制备质量浓度50%的溶液;将溶液喷淋于高速搅拌机中的聚偏氟乙烯(PVDF)中,高速搅拌均匀,鼓风干燥箱中90℃鼓风干燥2h,然后在温度80℃下用伽马射线辐照,辐照剂量1Mrad,得到预接枝混合料;所述预接枝混合料用异向啮合双螺杆挤出机挤出造粒,得到马来酸酐接枝聚偏氟乙烯(PVDF)。
其次,制备绝缘母粒:(1)将三烯丙基氰尿酸酯(TAC)溶于无水乙醇制备质量浓度50%的溶液;(2)将溶液喷淋于高速搅拌机中的聚偏氟乙烯(PVDF)和马来酸酐接枝聚偏氟乙烯(PVDF),高速搅拌均匀,鼓风干燥箱中105℃干燥2h,得到预混料;其中三烯丙基氰尿酸酯(TAC)、聚偏氟乙烯(PVDF)和马来酸酐接枝聚偏氟乙烯(PVDF)的质量比为2:100:20;(3)将预混料在室温条件下用伽马射线源C0-60辐照,辐照剂量5Mrad,得到预交联混合料;(4)所述预交联混合料用异向啮合双螺杆挤出机挤出造粒,对得到的粒料进行第二次辐照活化,辐照剂量1Mrad,得到绝缘母粒。
再者,制备电磁屏蔽母粒:将聚偏氟乙烯(PVDF)、导电碳黑和碳纳米管(质量比为8:2)、马来酸酐接枝聚偏氟乙烯和聚四氟乙烯微粉蜡按配比100:30:30:4,加入高速搅拌机中,高速搅拌为8分钟,搅拌温度80℃,得到预分散电磁屏蔽混合材料,所述的预分散电磁屏蔽混合料用异向啮合双螺杆挤出机挤出造粒,得到电磁屏蔽母粒。
最后,制备二层共挤电磁屏蔽氟塑料电绝缘波纹管材:将内绝缘层的绝缘母粒和电磁屏蔽母粒按出料质量比例1:1分别放入相应的挤出机中,二层共挤挤出氟塑料直管,将未完全冷却的氟塑料直管在波纹管设备模具中连续成型,循环冷水冷却定型,收卷机收卷,得到图2所示的管材。
实施例3
首先,制备马来酸酐接枝聚偏氟乙烯(PVDF):将马来酸酐溶于无水乙醇制备质量浓度40%的溶液;将溶液喷淋于高速搅拌机中的聚偏氟乙烯(PVDF)中,高速搅拌均匀,鼓风干燥箱中95℃鼓风干燥3.5h,然后在温度85℃下用伽马射线辐照,辐照剂量1.5Mrad,得到预接枝混合料;所述预接枝混合料用异向啮合双螺杆挤出机挤出造粒,得到马来酸酐接枝聚偏氟乙烯(PVDF)。
其次,制备绝缘母粒:(1)将异氰脲酸三烯丙酯(TAIC)溶于无水乙醇制备质量浓度40%的溶液;(2)将溶液喷淋于高速搅拌机中的聚偏氟乙烯(PVDF)和马来酸酐接枝聚偏氟乙烯(PVDF),高速搅拌均匀,鼓风干燥箱中102℃干燥3.5h,得到预混料;其中三烯丙基氰尿酸酯(TAC)、聚偏氟乙烯(PVDF)和马来酸酐接枝聚偏氟乙烯(PVDF)的质量比为1.5:100:15;(3)将预混料在室温条件下用伽马射线源Co-60辐照,辐照剂量4Mrad,得到预交联混合料;(4)所述预交联混合料用异向啮合双螺杆挤出机挤出造粒,对得到的粒料进行第二次辐照活化,辐照剂量0.8Mrad,得到绝缘母粒。
再者,制备电磁屏蔽母粒:将聚偏氟乙烯、导电碳黑和石墨烯(质量比例为9:1)、马来酸酐接枝聚偏氟乙烯和聚四氟乙烯微粉蜡按配比100:15:20:2,加入高速搅拌机中,高速搅拌为6分钟,搅拌温度60℃。得到预分散电磁屏蔽混合材料,所述的预分散电磁屏蔽混合料用异向啮合双螺杆挤出机造粒,得到电磁屏蔽母粒。
最后,制备二层共挤电磁屏蔽氟塑料电绝缘波纹管材:将外绝缘层的绝缘母粒和电磁屏蔽母粒按出料质量比例1:1分别放入相应的挤出机中,二层共挤挤出氟塑料直管,将未完全冷却的氟塑料直管在波纹管设备模具中连续成型,循环冷水冷却定型,收卷机收卷,得到图3所示的管材。
对比例1
除未添加马来酸酐接枝聚偏氟乙烯外,其他与实施例3相同。
对比例2
除绝缘母粒的原料未进行辐照预交联处理外,其他与实施例3相同。
对上述实施例和对比例所得管材参照《电磁屏蔽材料屏蔽效能测量方法》(GJB6190-2008)测试管材的电磁屏蔽材料屏蔽效能,测试条件:室温25℃,相度湿度70%;参照测试结果见表1。
表1.电磁屏蔽氟塑料电绝缘波纹管材性能表
实施例 | 内径/mm | 最小弯曲半径/mm | 电磁屏蔽效能/dB |
实施例1 | 12 | 32 | 65.4 |
实施例2 | 16 | 35 | 62.1 |
实施例3 | 20 | 40 | 63.7 |
对比例1 | 20 | 76 | 40 |
对比例2 | 20 | 72 | 43 |
由表1可知,采用本发明制备的一种多层共挤电磁屏蔽氟塑料电绝缘波纹管材,通过管材配方和制备方法的优化整合设计,该管材具有较好的电磁屏蔽效能,还具有较好的柔韧性等特点。
虽然已经通过示例对本发明的一些特定实施例进行了详细说明,但是本领域的技术人员应该理解,以上示例仅是为了进行说明,而不是为了限制本发明的范围。本领域的技术人员应该理解,可在不脱离本发明的范围和精神的情况下,对以上实施例进行修改。本发明的范围由所附权利要求来限定。
Claims (9)
1.一种多层共挤电磁屏蔽氟塑料电绝缘波纹管材,其特征在于,包括绝缘层和电磁屏蔽层,绝缘层的壁厚为0.1-2mm,电磁屏蔽层的壁厚为0.1-3mm;所述电磁屏蔽层包括可熔融氟塑料、电磁屏蔽材料、马来酸酐接枝可熔融含氢氟塑料和分散剂;所述绝缘层包含可熔融氟塑料、辐照交联剂和马来酸酐接枝可熔融含氢氟塑料;
所述多层共挤电磁屏蔽氟塑料电绝缘波纹管材的制备方法包括以下步骤:
制备绝缘母粒:(1)将辐照交联剂溶于无水乙醇制备质量浓度30-50%的溶液;(2)将溶液喷淋于高速搅拌机中的可熔融氟塑料和马来酸酐接枝可熔融含氢氟塑料,高速搅拌均匀,鼓风干燥箱中100-105℃干燥2-5h,得到预混料;(3)将预混料在室温条件下用伽马射线,辐照剂量3-5Mrad,得到预交联混合料;(4)所述预交联混合料用异向啮合双螺杆挤出机挤出造粒,对得到的粒料进行第二次辐照活化,辐照剂量0.5-1Mrad,得到绝缘母粒;
制备电磁屏蔽母粒:将可熔融氟塑料、电磁屏蔽材料、马来酸酐接枝可熔融含氢氟塑料和分散剂按配比100:(0.1-30):(10-30):(0.1-4),加入高速搅拌机中,高速搅拌为5-8分钟,搅拌温度为:40—80℃,得到预分散电磁屏蔽混合材料,所述的预分散电磁屏蔽混合料用异向啮合双螺杆挤出机挤出造粒,得到电磁屏蔽母粒;
制备管材:将绝缘母粒和电磁屏蔽母粒分别放入相应的挤出机中,多层共挤挤出氟塑料直管,将未完全冷却的氟塑料直管在波纹管设备模具中连续成型,循环冷水冷却定型,收卷机收卷。
2.根据权利要求1所述的多层共挤电磁屏蔽氟塑料电绝缘波纹管材,其特征在于,所述绝缘层为内绝缘层和/或外绝缘层,所述内绝缘层位于电磁屏蔽层的内侧,所述外绝缘层位于电磁屏蔽层的外侧。
3.根据权利要求1或2所述的多层共挤电磁屏蔽氟塑料电绝缘波纹管材,其特征在于,所述电磁屏蔽材料为碳纤维、导电碳黑、碳纳米管、石墨烯、黄铜短纤维、镍及镀镍石墨纤维、导电银粉、导电石墨和导电金属的一种或组合;所述分散剂为纳米二氧化硅、聚四氟乙烯微粉蜡的一种或组合。
4.根根据权利要求1或2所述的多层共挤电磁屏蔽氟塑料电绝缘波纹管材,其特征在于,所述辐照交联剂为异氰脲酸三烯丙酯(TAIC)、三烯丙基氰尿酸酯(TAC)中的一种或组合。
5.根据权利要求1所述的多层共挤电磁屏蔽氟塑料电绝缘波纹管材,其特征在于,所述可熔融氟塑料为全氟乙烯丙烯共聚物(FEP)、四氟乙烯-全氟烷氧基乙烯基醚共聚物(PFA)、聚三氟氯乙烯(PCTFE)、乙烯-三氟氯乙烯共聚物(ECTFE)、乙烯-四氟乙烯共聚物(ETFE)和聚偏氟乙烯(PVDF)中的一种或组合。
6.根据权利要求1所述的多层共挤电磁屏蔽氟塑料电绝缘波纹管材,其特征在于,所述马来酸酐接枝可熔融含氢氟塑料为马来酸酐接枝乙烯-四氟乙烯共聚物(ETFE)或马来酸酐接枝聚偏氟乙烯(PVDF)。
7.根据权利要求6所述的多层共挤电磁屏蔽氟塑料电绝缘波纹管材,其特征在于,所述可熔融氟塑料和马来酸酐接枝可熔融含氢氟塑料的组合为乙烯-四氟乙烯共聚物(ETFE)和马来酸酐接枝乙烯-四氟乙烯共聚物(ETFE),或者聚偏氟乙烯(PVDF)和马来酸酐接枝聚偏氟乙烯(PVDF)。
8.根据权利要求6所述的多层共挤电磁屏蔽氟塑料电绝缘波纹管材,其特征在于,所述马来酸酐接枝可熔融含氢氟塑料的制备方法包括以下步骤:将马来酸酐溶于无水乙醇制备质量浓度30-50%的溶液;将溶液喷淋于高速搅拌机中的可熔融含氢氟塑料中,高速搅拌均匀,鼓风干燥箱中90-100℃鼓风干燥2-5h,然后在温度80-90℃下用伽马射线辐照,辐照剂量1-2Mrad,得到预接枝混合料;所述预接枝混合料用异向啮合双螺杆挤出机挤出造粒,得到马来酸酐接枝可熔融含氢氟塑料。
9.根据权利要求1-8中任意一项所述的一种多层共挤电磁屏蔽氟塑料电绝缘波纹管材的制备方法,其特征在于,包括以下步骤:
制备绝缘母粒:(1)将辐照交联剂溶于无水乙醇制备质量浓度30-50%的溶液;(2)将溶液喷淋于高速搅拌机中的可熔融氟塑料和马来酸酐接枝可熔融含氢氟塑料,高速搅拌均匀,鼓风干燥箱中100-105℃干燥2-5h,得到预混料;(3)将预混料在室温条件下用伽马射线,辐照剂量3-5Mrad,得到预交联混合料;(4)所述预交联混合料用异向啮合双螺杆挤出机挤出造粒,对得到的粒料进行第二次辐照活化,辐照剂量0.5-1Mrad,得到绝缘母粒;
制备电磁屏蔽母粒:将可熔融氟塑料、电磁屏蔽材料、马来酸酐接枝可熔融含氢氟塑料和分散剂按配比100:(0.1-30):(10-30):(0.1-4),加入高速搅拌机中,高速搅拌为5-8分钟,搅拌温度为:40—80℃,得到预分散电磁屏蔽混合材料,所述的预分散电磁屏蔽混合料用异向啮合双螺杆挤出机挤出造粒,得到电磁屏蔽母粒;制备管材:将绝缘母粒和电磁屏蔽母粒分别放入相应的挤出机中,多层共挤挤出氟塑料直管,将未完全冷却的氟塑料直管在波纹管设备模具中连续成型,循环冷水冷却定型,收卷机收卷。
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