CN102083604A - 改进的使缆线脱气的方法 - Google Patents
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Abstract
本发明是使具有交联的半导体屏蔽层的电缆脱气的方法，所述交联的半导体屏蔽层由从以下物质制备或包含以下物质的组合物制成：(i)相I物质，其基本上由乙烯与具有4至20个碳原子的不饱和酯的极性共聚物组成，(ii)相II物质，其基本上由非极性低密度聚乙烯组成，和(iii)导电填料物质，其分散于相I物质和/或相II物质中。脱气温度大于70摄氏度。
Description
本发明涉及使电缆脱气的方法。更特别地，本发明涉及使电缆在高于常规使用温度的温度脱气的方法。
高压缆线的脱气时间通常是制备高压缆线的限速步骤。长达数月的脱气时间是常见的。降低脱气时间将直接影响生产力。
据信脱气时间由产生的交联副产物气体的量以及该气体从成品缆线中扩散出的速率决定。扩散的速率主要地取决于温度。
一些研究者试图通过减少用于使缆线组合物交联的过氧化物的量来解决脱气问题。然而，这种减少通常需要引入添加剂，而添加剂将负面影响缆线的电学性质。这是显著的缺点。
已经证明升高温度是不可接受的途径。特别地，使缆线脱气的加工温度限于约60摄氏度至70摄氏度，因为缆线在较高的温度往往自身熔接在一起(weld onto themselves)或变形。
期望在不会负面影响缆线的物理特征的情况下提高使缆线脱气的加工温度。特别地，期望将加工温度提高到高出60至70摄氏度的常规加工温度至少5摄氏度。甚至更期望使该温度提高至少10摄氏度。预期使加工温度提高10摄氏度将使一些缆线的脱气时间减少多达30％。
本发明是改进的使交联半导体屏蔽层在高于常规施用的脱气温度的温度脱气的方法。在第一种实施方式中，本发明方法包括使交联半导体屏蔽层在大于约70摄氏度的温度脱气的步骤。该温度可以大于或等于约75摄氏度。此外，该温度可以大于或等于约80摄氏度。
在第二种实施方式中，本发明方法包括使交联半导体屏蔽物层在比用来使常规的基于乙烯/不饱和酯共聚物的半导体屏蔽物组合物(semiconductive shield composition)脱气的温度高至少约5摄氏度的温度脱气的步骤。
对于所描述的两种实施方式，该方法优选地使用在WO/2007/092454中所描述的半导体屏蔽物组合物。所述组合物包括
(i)相I物质，其基本上由乙烯与具有4至20个碳原子的不饱和酯的极性共聚物组成；
(ii)相II物质，其基本上由非极性低密度聚乙烯组成；和
(iii)导电填料物质，其分散在所述相I物质和/或所述相II物质中，其量足以等于或大于为使其在相I和相II物质中产生连续传导网络(continuous conducting network)所需要的量。
相I物质基本上由乙烯与不饱和酯的极性共聚物组成。该极性共聚物通常通过高压法制备。常规的高压法由Introduction to Polymer Chemistry，Stille，Wiley and Sons，NewYork，1962，第149-151页所描述。所述高压法典型地为在管式反应器或搅拌高压釜中进行的自由基引发的聚合反应。在搅拌高压釜中，压力为10,000磅每平方英寸(psi)至30,000psi，温度为175摄氏度至250摄氏度，而在管式反应器中，压力为25,000psi至45,000psi，温度为200摄氏度至350摄氏度。
不饱和酯可以为丙烯酸烷基酯、甲基丙烯酸烷基酯和羧酸乙烯酯。所述烷基基团可以具有1至8个碳原子，并且优选地具有1至4个碳原子。所述羧酸酯基团可以具有2至8个碳原子，并且优选地具有2至5个碳原子。
归属于酯共聚单体的共聚物部分可以占共聚物重量的约10重量％至约55重量％，并且优选为约15重量％至约30重量％。关于摩尔百分率，所述酯共聚单体的存在量可以为5摩尔％至30摩尔％。所述酯可以具有4至20个碳原子，并且优选地具有4至7个碳原子。
乙烯基酯(或碳酸酯)的实例为醋酸乙烯基酯、丁酸乙烯基酯、新戊酸乙烯基酯；新壬酸乙烯基酯；新癸酸乙烯基酯；和2-乙基己酸乙烯基酯。醋酸乙烯基酯是优选的。丙烯酸酯和甲基丙烯酸酯的实例是甲基丙烯酸十二烷基酯；甲基丙烯酸十四烷基酯；甲基丙烯酸棕榈酯；甲基丙烯酸十八烷基酯；3-甲基丙烯氧基-丙基三甲氧基硅烷；3-甲基丙烯氧基丙基三乙氧基硅烷；甲基丙烯酸环己基酯；甲基丙烯酸正己基酯；甲基丙烯酸异癸酯；甲基丙烯酸2-甲氧基乙基酯；甲基丙烯酸四氢糠基酯；甲基丙烯酸辛酯；甲基丙烯酸2-苯氧基乙基酯；甲基丙烯酸异冰片酯；甲基丙烯酸异辛基酯；甲基丙烯酸辛酯；甲基丙烯酸异辛酯；甲基丙烯酸油基酯；丙烯酸乙酯；丙烯酸甲酯；丙烯酸叔丁酯；丙烯酸正丁酯；和丙烯酸2-乙基己基酯。丙烯酸甲酯、丙烯酸乙酯、和丙烯酸正丁酯或丙烯酸叔丁酯是优选的。例如，烷基基团可以以氧烷基三烷氧基硅烷取代。
本申请共聚物的密度可以为0.900克每立方厘米至0.990克每立方厘米，并且优选为0.920克每立方厘米至0.970克每立方厘米。本发明共聚物的熔体指数也可以为0.1克每10分钟至100克每10分钟，所述熔体指数优选地为1克每10分钟至50克每10分钟，并且更优选为5克每10分钟至21克每10分钟。
相I物质在复合材料中的存在量可以为10重量％至80重量％，基于复合材料的重量，并且优选地，其存在量为20重量％至60重量％。
相II物质基本上由非极性低密度聚乙烯(LDPE)组成，所述LDPE作为乙烯的均聚物制备并且通常通过高压法制备。如前所述，常规的高压法由Introduction to Polymer Chemistry，Stille，Wiley and Sons，New York，1962，第149至151页所描述。高压法典型地为在管式反应器或搅拌高压釜中进行的自由基引发的聚合反应。在搅拌高压釜中，压力为10,000psi至30,000psi，温度为175摄氏度至250摄氏度，而在管式反应器中，压力为25,000psi至45,000psi，温度为200摄氏度至350摄氏度。
这些LDPE聚合物的密度通过ASTM D-792测量为约0.910克每立方厘米至约0.940克每立方厘米。
优选地，非极性低密度聚乙烯的多分散性(Mw/Mn)为1.1至10。Mw定义为重均分子量，Mn定义为数均分子量。优选地，Mw为10,000至1,000,000。它们的熔体指数也可以为0.25克每10分钟至30克每10分钟，优选地，可以为1克每10分钟至20克每10分钟，并且更优选地，可以为5克每10分钟至10克每10分钟。
相II物质在复合材料中的存在量可以为10重量％至80重量％，基于复合材料的重量，并且优选地所述存在量为20重量％至60重量％。
任选地，可以将其它聚合材料的另外的相引入到复合材料中，如果它们具有与相I物质或相II物质的性质相符合的性质。
优选地，相II物质的熔点大于相I物质的熔点。
本申请聚合物可以通过使树脂变成可水解的，以湿气固化制备，其通过加入可水解基团如-Si(OR)3来完成，其中R是经共聚合或接枝键接于树脂结构的烃基基团。适宜的接枝剂是有机过氧化物，如二枯基过氧化物；2，5-二甲基-2，5-二(叔丁基过氧)己烷；叔丁基枯基过氧化物；和2，5-二甲基-2，5-二(叔丁基过氧)己烷-3。二枯基过氧化物是优选的。可以加入可水解基团，例如，其通过使乙烯与具有一个或多个-Si(OR)3基团的烯键式不饱和化合物(如乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、和γ-甲基丙烯氧基丙基三甲氧基-硅烷)共聚合或通过在上述有机过氧化物存在的情况下将这些硅烷化合物接枝到树脂上实现。可水解树脂随后在硅烷醇缩合催化剂存在的情况下通过湿气交联，所述硅烷醇缩合催化剂如二月桂酸二丁基锡、马来酸二辛基锡、二醋酸二丁基锡、醋酸锡、环烷酸铅、和辛酸锌。二月桂酸二丁基锡是优选的。
导电填料物质(导电粒子)可以是通常用于半导体屏蔽物的常规导电炭黑。这些导电粒子通常已由颗粒炭黑提供。有用的炭黑的表面积可以为50至1000平方米每克。所述表面积根据ASTM D 4820-93a(多点式B.E.T.氮吸附)确定。在WO/2007/092454中，将炭黑描述为，在半导体屏蔽物组合物中的使用量为10重量％至50重量％，基于组合物的重量，并且优选地使用量为15重量％至45重量％，更优选地使用量为25重量％至35重量％。这可以称为导电填料载量，并且最优选为27重量％至33重量％。
尽管本发明可以使用WO/2007/092454的炭黑载量，但是当施用本发明的方法时，炭黑载量的使用量可以低于在常规半导体屏蔽物组合物中的使用量。如此并且当期望较低的炭黑载量时，优选地，炭黑的存在量小于25重量％；更优选地，其存在量小于15重量％；并且最优选地，其存在量小于10重量％。
标准电导率炭黑和高电导率炭黑都可以使用，其中标准电导率炭黑是优选的。导电炭黑的实例是如下描述的等级：ASTM N550、N472、N351、N110、Ketjen黑、炉黑、和乙炔黑。
炭黑是呈球形胶体微粒以及凝结的颗粒聚集体形式的单质碳，其通过烃类的热分解制备。尽管与石墨相比，炭黑较为无序，但是炭黑的微观结构本质上是石墨类的。炭黑的关键特征之一是高的多孔度并且在炭黑粒子的核心是中空的。炭黑称为本征半导体。
也可以使用碳纳米管。
也可以使用除了炭黑或碳纳米管以外的导电填料。实例是金属粒子、富勒烯、和导电聚合物(如聚乙炔、聚苯、聚吡咯、聚噻吩、和聚苯胺)。
任选地，丙烯腈和丁二烯的共聚物(其中丙烯腈的存在量为20重量％至60重量％，基于共聚物的重量，并且优选地存在量为30重量％至40重量％)可以包括在半导体屏蔽物组合物中。该共聚物通常用于可剥离绝缘屏蔽物中，而非导体屏蔽物或绞线屏蔽物(strand shield)中。该共聚物也称为丁腈橡胶或丙烯腈/丁二烯共聚物橡胶。其密度可以为，例如，0.98克每立方厘米，门尼粘度可以为(ML 1+4)50。视需要，可以用丁腈橡胶替代硅橡胶。
任选地，本发明的组合物可以包含其它的聚烯烃(包括乙烯α-烯烃共聚物)，其含量可以小于约25重量％，基于存在的全部聚合物的重量。
可以引入组合物的示例性的常规添加剂为抗氧化剂、偶联剂、紫外线吸收剂或稳定剂、抗静电剂、颜料、染料、成核剂、增强填料或聚合物添加剂、增滑剂、增塑剂、加工助剂、润滑剂、粘度控制剂、增粘剂、抗粘连剂、表面活性剂、增量油、金属钝化剂、稳压剂、阻燃填料及添加剂、交联剂、促进剂、催化剂、和烟雾抑制剂。
Claims (4)
1.一种使电缆脱气的方法，其包括以下步骤：
(a)选择交联的半导体屏蔽物组合物，其包括
(i)相I物质，其基本上由乙烯与具有4至20个碳原子的不饱和酯的极性共聚物组成；
(ii)相II物质，其基本上由非极性低密度聚乙烯组成；和
(iii)导电填料物质，其分散在所述相I物质和/或所述相II物质中，其量足以等于或大于为使其在所述相I和相II物质中产生连续传导网络所需要的量；
(b)将所述交联的半导体屏蔽物组合物涂覆在金属导体上，产生半导体屏蔽层；
(c)使所述半导体屏蔽层交联，产生具有交联的半导体屏蔽层的电缆；
(d)使所述电缆在大于70摄氏度的脱气温度脱气。
2.权利要求1中所述的方法，其中所述脱气温度大于75摄氏度。
3.权利要求1中所述的方法，其中所述脱气温度大于80摄氏度。
4.权利要求1-3中任一项所述的方法，其中所述相II物质的熔点大于所述相I物质的熔点。
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| US7764908P | 2008-07-02 | 2008-07-02 | |
| US61/077,649 | 2008-07-02 | ||
| PCT/US2009/049376 WO2010002973A1 (en) | 2008-07-02 | 2009-07-01 | Improved method for degassing cables |
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| EP (1) | EP2303536A1 (zh) |
| JP (1) | JP2011527088A (zh) |
| KR (1) | KR20110039316A (zh) |
| CN (1) | CN102083604A (zh) |
| BR (1) | BRPI0910186A2 (zh) |
| CA (1) | CA2729561A1 (zh) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105097124A (zh) * | 2015-09-23 | 2015-11-25 | 陈薇 | 一种电缆光缆数据电缆一体化总线及其制备方法 |
| CN105139948A (zh) * | 2015-09-23 | 2015-12-09 | 陈薇 | 一种防火型电缆光缆数据电缆一体化总线及其制备方法 |
| CN105493202A (zh) * | 2013-09-20 | 2016-04-13 | 陶氏环球技术有限责任公司 | 交联电力电缆的脱气方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10689502B2 (en) * | 2015-05-22 | 2020-06-23 | Dow Global Technologies Llc | Processes for preparing cables with a crosslinked insulation layer and cables for same |
| CN104979051B (zh) * | 2015-06-03 | 2017-01-11 | 浙江万马股份有限公司 | 66-500kV交联电缆短脱气在线处理工艺 |
| CN106128653A (zh) * | 2016-08-15 | 2016-11-16 | 河南开启电力实业有限公司 | 中高压电缆交联生产线用除气装置 |
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- 2009-07-01 MX MX2010014544A patent/MX2010014544A/es not_active Application Discontinuation
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| TW201007774A (en) | 2010-02-16 |
| EP2303536A1 (en) | 2011-04-06 |
| JP2011527088A (ja) | 2011-10-20 |
| KR20110039316A (ko) | 2011-04-15 |
| MX2010014544A (es) | 2011-03-29 |
| WO2010002973A1 (en) | 2010-01-07 |
| CA2729561A1 (en) | 2010-01-07 |
| BRPI0910186A2 (pt) | 2016-01-19 |
| US20110097898A1 (en) | 2011-04-28 |
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