CN117567824A - 一种钙掺杂氟树脂电缆及其制备方法 - Google Patents

一种钙掺杂氟树脂电缆及其制备方法 Download PDF

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CN117567824A
CN117567824A CN202311523853.9A CN202311523853A CN117567824A CN 117567824 A CN117567824 A CN 117567824A CN 202311523853 A CN202311523853 A CN 202311523853A CN 117567824 A CN117567824 A CN 117567824A
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fluororesin
calcium
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徐楚楠
宋玉全
任一鸣
刘洪平
潘梦
强晨晨
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Wuhu Jiahong New Material Co ltd
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Abstract

本发明公开了一种钙掺杂氟树脂电缆及其制备方法，本发明的一种钙掺杂氟树脂电缆，所述电缆绝缘材料采用钙掺杂氟树脂制成，所述钙掺杂氟树脂包括重量份数计的如下组分组成：氟树脂1份，氢氧化钙0.06～0.12份，抗氧化剂0.008～0.01份，润滑剂0.05～0.06份，碳纤维0.05～0.08份，硅灰石0.05～0.08份。本发明的一种钙掺杂氟树脂电缆的制备方法，包括如下步骤：(1)用胶体磨将氟树脂磨细，然后用筛子过筛；(2)过筛的氟树脂和氢氧化钙以及其他添加剂在混合器中进行充分混合；(3)送入熔融工段进行热加工制备不同种类的电缆。本发明可加工性强，制备的电缆性能更优越，安全环保。

Description

一种钙掺杂氟树脂电缆及其制备方法
技术领域
本发明涉及高分子化合物技术领域，具体为一种钙掺杂氟树脂电缆及其制备方法。
背景技术
氟树脂是部分或全部氢被氟取代的烷烃聚合物，主要有聚四氟乙烯(PTFE)、聚三氟氯乙烯(PCTEF)、聚偏氟乙烯(PVDF)、聚氟乙烯(PVF)、聚全氟乙丙烯(FEP)、乙烯-四氟乙烯共聚物(ETFE)、四氟乙烯与全氟(正)丙基乙烯基醚的共聚物(PFA)、四氟乙烯-六氟丙烯-偏氟乙烯的共聚物(THV)等。
氟树脂具有优异的介电性能和耐高低温、耐化学腐蚀、电绝缘性好、防水、表面不粘、低摩擦系数、良好的自润滑性等性能。目前，已广泛应用于航空、航天、化工、电子、电气、半导体、电缆等工业领域。但是在加工过程中，氟树脂在高温度和高剪切作用下容易分解产生氟化氢酸气体，该气体具有强腐蚀性和毒性，极易对设备产生腐蚀损坏，并对操作人员产生身体伤害。氟化钙作为一种优良的添加剂，被广泛的用于电缆(CN110551356,CN105603279)，光纤传导等技术领域。本发明通过加入氢氧化钙，与加工过程产生的氟化氢发生中和反应生成氟化钙(反应式1)，不需要额外加入氟化钙，同时极大的降低了氟化氢的排放，生成的水被高温蒸发除去。少量没有反应的氢氧化钙并没有影响相关产品的性能。
Ca(OH)2+HF→CaF2+H2O 反应式1
目前，缺乏一种能够去除氢氟酸气体的氟树脂加工工艺。
发明内容
为了解决现有合成技术的不足，本发明的目的是一种能够去除在高温环境下氟塑料加工产生的氢氟酸的钙掺杂氟树脂加工工艺，以解决上述背景技术中提出的问题。
为了实现上述目的，本发明采用如下技术方案：本发明的一种钙掺杂氟树脂电缆，由内向外依次包括导体、电缆绝缘和电缆护套，所述电缆绝缘材料采用钙掺杂氟树脂制成，所述钙掺杂氟树脂包括重量份数计的如下组分组成：
本发明的一种钙掺杂氟树脂电缆的制备方法，包括如下步骤：(1)用胶体磨将氟树脂磨细，然后用筛子过筛；
(2)过筛的氟树脂和氢氧化钙在混合器中进行充分混合；
(3)送入熔融工段进行热加工制备不同种类的电缆。
进一步地，在步骤(1)中，筛子的目数为30-80目。
进一步地，在步骤(2)中，所述氟树脂为聚四氟乙烯PTFE260、聚三氟氯乙烯PCTEF180、聚偏氟乙烯PVDF150、聚氟乙烯PVF107、聚全氟乙丙烯FEP255-270、乙烯-四氟乙烯共聚物ETFE260-270中的一种或多种的组合。
更进一步地，在步骤(2)中，所述抗氧化剂为N,N-双[β(3,5-二叔丁基-4-羟基苯基)丙酮]肼，所述润滑剂为聚四氟乙烯蜡。
进一步地，在步骤(2)中，所述N,N-双[β(3,5-二叔丁基-4-羟基苯基)丙酮]肼的型号为CHINOX 1024；所述聚四氟乙烯蜡的粒径3～5μm；所述碳纤维的尺寸为20μm；所述硅灰石的尺寸为20μm。
进一步地，在步骤(2)中，所述氟树脂和氢氧化钙的质量比为1：0.06～0.12。
更进一步地，在步骤(2)中，所述混合器中的混合时间为5-10min。
进一步地，在步骤(3)中，所述熔融温度为100～330℃。
进一步地，在步骤(3)中，所述熔融时间为10～20min。
有益效果：本发明可加工性强，制备的电缆性能更优越，安全环保。
与现有技术相比，本发明具有如下优点：
(1)通过加入氢氧化钙，与加工过程产生的氟化氢发生中和反应生成氟化钙，极大的降低了氟化氢的排放，生成的水被高温蒸发除去。再进一步加工成电缆的时，不需要额外加入氟化钙。氟化氢气体排放减少95％以上。
(2)通过加入抗氧化剂，在高温加工时，可以有效防止材料的氧化，提高材料的稳定性。
(3)通过加入润滑剂，即使在熔融状态下，依然能够帮助其他填料充分混合，同时他本身为短聚合链的聚四氟乙烯，也同属于氟树脂。
(4)通过加入碳纤维和硅灰石，这两种材料都属于无机填料，可以提高复合材料的机械性能，强度与韧性，提高产品的耐久度。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
本发明的一种钙掺杂氟树脂电缆，由内向外依次包括导体、电缆绝缘和电缆护套，所述电缆绝缘材料采用钙掺杂氟树脂制成，所述钙掺杂氟树脂包括重量份数计的如下组分组成：
本发明的一种钙掺杂氟树脂电缆及其制备方法，包括如下步骤：
(1)用胶体磨将氟树脂磨细，然后用筛子过筛，筛子的目数为50目。
(2)过筛的氟树脂和氢氧化钙在混合器中进行充分混合，所述氟树脂为聚四氟乙烯PTFE260。所述氟树脂和氢氧化钙的质量比为1：0.12。所述混合器中的混合时间为10min。所述熔融温度为100℃。
(3)送入熔融工段进行热加工制备不同种类的电缆。所述熔融时间为20min。
实施例2
实施例2与实施例1的区别在于：本发明的一种钙掺杂氟树脂电缆，由内向外依次包括导体、电缆绝缘和电缆护套，所述电缆绝缘材料采用钙掺杂氟树脂制成，所述钙掺杂氟树脂包括重量份数计的如下组分组成：
本发明的一种钙掺杂氟树脂电缆及其制备方法，包括如下步骤：
在步骤(1)中，用胶体磨将氟树脂磨细，然后用筛子过筛，筛子的目数为30目。
在步骤(2)中，过筛的氟树脂和氢氧化钙在混合器中进行充分混合，所述氟树脂为聚三氟氯乙烯PCTEF180。所述氟树脂和氢氧化钙的质量比为1：0.09。所述混合器中的混合时间为5min。所述熔融温度为230℃。
在步骤(3)中，送入熔融工段进行热加工制备不同种类的电缆。所述熔融时间为15min。
实施例3
实施例3与实施例1的区别在于：本发明的一种钙掺杂氟树脂电缆，由内向外依次包括导体、电缆绝缘和电缆护套，所述电缆绝缘材料采用钙掺杂氟树脂制成，所述钙掺杂氟树脂包括重量份数计的如下组分组成：
本发明的一种钙掺杂氟树脂电缆及其制备方法，包括如下步骤：
在步骤(1)中，用胶体磨将氟树脂磨细，然后用筛子过筛，筛子的目数为80目。
在步骤(2)中，过筛的氟树脂和氢氧化钙在混合器中进行充分混合，所述氟树脂为聚偏氟乙烯PVDF150和聚氟乙烯PVF107的组合。所述氟树脂和氢氧化钙的质量比为1：0.06，其他添加剂不变。所述混合器中的混合时间为8min。所述熔融温度为330℃。
在步骤(3)中，送入熔融工段进行热加工制备不同种类的电缆。所述熔融时间为10min。
实施例4
实施例4与实施例1的区别在于：在步骤(2)中，过筛的氟树脂和氢氧化钙在混合器中进行充分混合，所述氟树脂为聚全氟乙丙烯FEP255-270和乙烯-四氟乙烯共聚物ETFE260-270的组合。所述氟树脂和氢氧化钙的质量比为1：0.06。所述混合器中的混合时间为8min。所述熔融温度为330℃。
试验例1
乙烯-四氟乙烯共聚物(ETFE)加工工艺
首先用用胶体磨将乙烯-四氟乙烯磨细，然后用40目筛子过筛，进一步的，过筛的乙烯-四氟乙烯树脂，然后分别将纯乙烯-四氟乙烯树脂与Ca(OH)2含量为0％、5％、10％、15％和20％送入熔融工段，于200℃熔融15min，得到不同掺杂比例的乙烯-四氟乙烯树脂，在熔融混合的过程时，将混合环境密封，然后开孔通过气管连接若干串联的1L水的容器中，第一个容器上装有抽气泵与ph检测仪。随后对混合料进行机械性能的测试如表1所示。
表1
试验例2
聚全氟乙丙烯(FEP)加工工艺
首先用用胶体磨将聚全氟乙丙烯磨细，然后用40目筛子过筛，进一步的，过筛的聚全氟乙丙烯树脂，然后分别将纯聚全氟乙丙烯树脂与Ca(OH)2粉末含量为0％、5％、10％、15％和20％送入熔融工段，于200℃熔融15min，得到不同掺杂比例的聚全氟乙丙烯树脂，在熔融混合的过程时，将混合环境密封，然后开孔通过气管连接若干串联的1L水的容器中，第一个容器上装有抽气泵与ph检测仪。随后对混合料进行机械性能的测试如表2所示。
表2
通过试验例1和试验例2可知，不同比例制得的材料进行性能测试，测试结果由表1，表2所示，在没有添加Ca(OH)2粉末时，实施例1和实施例2所测的水溶液的确为酸性，也就意味着确实有酸性气体产生；随着Ca(OH)2粉的添加，可以发现熔融指数在不断的下降，比重变化不大，抗拉强度与断裂伸长率有所下降，水溶液中的PH值在缓慢的升高，其原因是Ca(OH)2粉的添加，在高温熔融时产生的酸性气体直接被添加的Ca(OH)2粉中和吸收，所以水溶液的PH值显示中性。但当Ca(OH)2粉的含量达到20％时，可以发现成品的机械强度大大减弱，抗拉强度低至10MPa左右，不符合工业应用。可以看出，在15％左右的Ca(OH)2混合比例既能够中和酸性气体防止氢氟酸对设备的腐蚀，又能够满足工业应用的基本特性。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，本发明要求保护范围由所附的权利要求书、说明书及其等效物界定。

Claims (10)

1.一种钙掺杂氟树脂电缆，由内向外依次包括导体、电缆绝缘和电缆护套，其特征在于：所述电缆绝缘材料采用钙掺杂氟树脂制成，所述钙掺杂氟树脂包括重量份数计的如下组分组成：
2.一种权利要求1所述的钙掺杂氟树脂电缆的制备方法，其特征在于包括如下步骤：(1)用胶体磨将氟树脂磨细，然后用筛子过筛；
(2)过筛的氟树脂和氢氧化钙在混合器中进行充分混合；
(3)送入熔融工段进行热加工制备不同种类的电缆。
3.根据权利要求2所述的钙掺杂氟树脂电缆的制备方法，其特征在于：在步骤(1)中，筛子的目数为30-80目。
4.根据权利要求2所述的钙掺杂氟树脂电缆的制备方法，其特征在于：在步骤(2)中，所述氟树脂为聚四氟乙烯PTFE260、聚三氟氯乙烯PCTEF180、聚偏氟乙烯PVDF150、聚氟乙烯PVF107、聚全氟乙丙烯FEP255-270、乙烯-四氟乙烯共聚物ETFE260-270中的一种或多种的组合。
5.根据权利要求2所述的钙掺杂氟树脂电缆的制备方法，其特征在于：在步骤(2)中，所述抗氧化剂为N,N-双[β(3,5-二叔丁基-4-羟基苯基)丙酮]肼，所述润滑剂为聚四氟乙烯蜡。
6.根据权利要求5所述的钙掺杂氟树脂电缆的制备方法，其特征在于：在步骤(2)中，所述N,N-双[β(3,5-二叔丁基-4-羟基苯基)丙酮]肼的型号为CHINOX 1024；所述聚四氟乙烯蜡的粒径3～5μm；所述碳纤维的尺寸为20μm；所述硅灰石的尺寸为20μm。
7.根据权利要求2所述的钙掺杂氟树脂电缆的制备方法，其特征在于：在步骤(2)中，所述氟树脂和氢氧化钙的质量比为1：0.06～0.12。
8.根据权利要求2所述的钙掺杂氟树脂电缆的制备方法，其特征在于：在步骤(2)中，所述混合器中的混合时间为5-10min。
9.根据权利要求2所述的钙掺杂氟树脂电缆的制备方法，其特征在于：在步骤(3)中，所述熔融温度为100～330℃。
10.根据权利要求2所述的钙掺杂氟树脂电缆的制备方法，其特征在于：在步骤(3)中，所述熔融时间为10～20min。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103803932A (zh) * 2014-01-21 2014-05-21 济南大学 一种氟石膏装饰隔墙板的制备方法
CN108047612A (zh) * 2018-01-25 2018-05-18 长园电子（东莞）有限公司 一种氟塑料电线电缆及其制备方法
CN110483925A (zh) * 2018-05-14 2019-11-22 日立金属株式会社 热塑性氟树脂组合物、电线和电缆
JP2020140771A (ja) * 2019-02-26 2020-09-03 日立金属株式会社 電線の製造方法およびケーブルの製造方法
CN117050443A (zh) * 2023-08-15 2023-11-14 广东天诚密封件股份有限公司 一种具有高伸长率的氟橡胶及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103803932A (zh) * 2014-01-21 2014-05-21 济南大学 一种氟石膏装饰隔墙板的制备方法
CN108047612A (zh) * 2018-01-25 2018-05-18 长园电子（东莞）有限公司 一种氟塑料电线电缆及其制备方法
CN110483925A (zh) * 2018-05-14 2019-11-22 日立金属株式会社 热塑性氟树脂组合物、电线和电缆
JP2020140771A (ja) * 2019-02-26 2020-09-03 日立金属株式会社 電線の製造方法およびケーブルの製造方法
CN117050443A (zh) * 2023-08-15 2023-11-14 广东天诚密封件股份有限公司 一种具有高伸长率的氟橡胶及其制备方法

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