CN105209534B - 具有电压稳定内层的经涂布导体 - Google Patents
具有电压稳定内层的经涂布导体 Download PDFInfo
- Publication number
- CN105209534B CN105209534B CN201480021091.5A CN201480021091A CN105209534B CN 105209534 B CN105209534 B CN 105209534B CN 201480021091 A CN201480021091 A CN 201480021091A CN 105209534 B CN105209534 B CN 105209534B
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- China
- Prior art keywords
- coated conductor
- layer
- polymeric compositions
- internal layer
- triazine
- Prior art date
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 15
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
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- HGVPOWOAHALJHA-UHFFFAOYSA-N ethene;methyl prop-2-enoate Chemical compound C=C.COC(=O)C=C HGVPOWOAHALJHA-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B1/08—Tubular products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/06—Polyethene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract
本发明公开具有改进击穿强度的聚合组合物。所述聚合组合物含有聚烯烃和电压稳定剂，所述电压稳定剂选自三种特定三嗪化合物的群组中的一者或多者。当作为用于电力电缆的绝缘层施加时本发明聚合组合物展示改进的击穿强度。
Description
相关申请的参考
本申请要求2013年4月18日提交的美国临时申请第61/813,320号的权益。
背景技术
典型电力电缆在由一个或多个聚合材料层包围的电缆芯中包括一个或多个导体。中压(6kV到36kV)、高压(大于36kV)以及超高压(大于220kV)电缆典型地包括由内部半导体层、随后绝缘层和然后外部半导体层以及最外层(或护套)包围的芯。
电缆系统的承载力部分受离开导体的热传递限制。聚烯烃，如聚乙烯，常常用于绝缘层和/或半导体层中。聚乙烯具有低介电常数和相对较高的电击穿强度。
已知的是增加电力电缆中的绝缘层的电击穿强度的用于聚烯烃组合物的电压稳定剂。然而，常规电压稳定剂(如多环芳香族物，例如并苯家族)与聚烯烃具有不佳相容性。所属领域认识到对与聚烯烃相容的用于(i)电缆绝缘材料的增加电击穿强度，(ii)现有电缆设计的增加可靠性和/或(iii)提供能够递送增加量的能量的高应力设计的电压稳定剂的持续需要。
发明内容
一个实施例是一种经涂布导体，其包含：
导体；
最外不透明层；
位于所述导体与所述最外层之间的内层，所述内层包含聚合组合物，所述聚合组合物包含：
聚烯烃；和
三嗪，其选自由具有结构(I)、(II)或(III)中的一个的化合物和其两者或更多者的组合组成的群组：
附图说明
图1是根据本发明的一个实施例的电力电缆的透视图。
具体实施方式
本发明提供一种聚合组合物。聚合组合物包括(i)聚合组分，(ii)电压稳定剂，以及(iii)任选地其它添加剂。本发明进一步提供包含所述聚合组合物的经涂布导体。
聚合组分
聚合组分可包括热塑物和/或热固性材料(如硅酮橡胶)。聚合组分可为交联或可为非交联。适合热塑物的非限制性实例包括聚氨基甲酸酯、聚烯烃、聚缩醛、聚碳酸酯、乙烯基聚合物、聚酰胺、聚酰亚胺、丙烯酸聚合物、聚苯乙烯、聚砜、聚醚酮、纤维素材料、聚酯、聚醚、氟聚合物和其共聚物(如烯烃-乙烯基共聚物、烯烃-烯丙基共聚物以及聚醚与聚酰胺的共聚物)。乙烯基聚合物的实例包括聚氯乙烯、聚乙酸乙烯酯、氯乙烯/乙酸乙烯酯共聚物、聚乙烯醇以及聚乙烯缩醛。
当需要使用交联聚合组分时，交联可通过以下非限制性程序中的一种或多种实现：自由基交联(例如过氧化物交联)、辐射交联(例如电子加速器、γ射线、高能量辐射(如X射线、微波等))、热交联和/或湿气固化交联(例如硅烷接枝)。
在一个实施例中，聚合组分是聚烯烃。适合聚烯烃的非限制性实例是含有一个或多个C2-C20α-烯烃的均聚物和共聚物。出于本发明的目的，乙烯被视为是α-烯烃。适合α-烯烃的非限制性实例包括乙烯、丙烯、异丁烯、1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯以及1-辛烯。适合聚烯烃的非限制性实例包括乙烯类聚合物、丙烯类聚合物以及其组合。“乙烯类聚合物”或“聚乙烯”和类似术语是含有至少50摩尔百分比(mol％)衍生自乙烯的单元的聚合物。“丙烯类聚合物”或“聚丙烯”和类似术语是含有至少50摩尔百分比衍生自丙烯的单元的聚合物。
在一个实施例中，聚合组分是乙烯类聚合物。乙烯类聚合物可为乙烯均聚物或乙烯/α-烯烃互聚物。按互聚物的重量计，α-烯烃含量是约5wt％或约10wt％、或约15wt％、或约20wt％、或约25wt％到小于50wt％、或小于约45wt％、或小于约40wt％、或小于约35wt％。α-烯烃含量通过13C核磁共振(NMR)光谱法使用兰多尔(Randall)(《大分子化学物理评论》(Rev.Macromol.Chem.Phys.)，C29(2和3))中描述的程序测量。一般来说，互聚物的α-烯烃含量越高，密度越低并且互聚物越非晶形，并且这可翻译成保护性绝缘层的合乎需要的物理和化学特性。
α-烯烃是C3-20线性、支化或环状α-烯烃。适合C3-20α-烯烃的非限制性实例包括丙烯、1-丁烯、4-甲基-1-戊烯、1-己烯、1-辛烯、1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯以及1-十八碳烯。α-烯烃还可含有环状结构，如环己烷或环戊烷，产生如3-环己基-1-丙烯(烯丙基环己烷)和乙烯基环己烷的α-烯烃。尽管在术语的经典意义上不是α-烯烃，但出于本发明的目的，某些环状烯烃，如降冰片烯和相关烯烃，特别是5-亚乙基-2-降冰片烯，是α-烯烃并且可代替上文所描述的α-烯烃中的一些或全部使用。类似地，出于本发明的目的，苯乙烯和其相关烯烃(例如α-甲基苯乙烯等)是α-烯烃。适合乙烯类聚合物的非限制性实例包括以下共聚物：乙烯/丙烯、乙烯/丁烯、乙烯/1-己烯、乙烯/1-辛烯、乙烯/苯乙烯、乙烯-乙酸乙烯酯、乙烯-丙酸乙烯酯、乙烯-异丁酸乙烯酯、乙烯-乙烯醇、乙烯丙烯酸甲酯、乙烯-丙烯酸乙酯、乙烯-甲基丙烯酸乙酯、乙烯/丙烯酸丁酯共聚物(EBA)、乙烯-烯丙基苯、乙烯-烯丙基醚以及乙烯丙烯醛；乙烯-丙烯(EPR)或乙烯-丙烯-二烯(EPDM)橡胶；天然橡胶；丁基橡胶等。
适合三元共聚物的非限制性实例包括乙烯/丙烯/1-辛烯、乙烯/丙烯/丁烯、乙烯/丁烯/1-辛烯、乙烯/丙烯/二烯单体(EPDM)以及乙烯/丁烯/苯乙烯。共聚物/互聚物可为无规或嵌段。
乙烯类聚合物可为高密度聚乙烯(HDPE)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)和/或极低密度聚乙烯(VLDPE)。用于本发明的实践的乙烯类聚合物可单独或与一种或多种其它乙烯类聚合物(例如“彼此不同的两种或更多种乙烯类聚合物的掺合物”)组合使用，这意味着乙烯类聚合物借助于如以下的至少一种特性而不常见：单体/共聚单体组成和含量、熔融指数、熔融温度、支化度、制备的催化方法等。如果乙烯类聚合物是两种或更多种乙烯类聚合物的掺合物，那么乙烯类聚合物可通过任何反应器中或反应器后方法掺合。反应器可装有相同催化剂但在不同条件(例如不同反应物浓度、温度、压力等)下操作或在相同条件下操作但装有不同催化剂。
用高压方法制得的乙烯类聚合物的实例包括(但不限于)低密度聚乙烯(LDPE)、乙烯乙酸乙烯酯共聚物(EVA)、乙烯丙烯酸乙酯共聚物(EEA)以及乙烯硅烷丙烯酸酯三元共聚物。
乙烯类聚合物的非限制性实例包括极低密度聚乙烯(VLDPE)(例如由陶氏化学公司(The Dow Chemical Company)制造的乙烯/1-己烯聚乙烯)、均质支化、线性乙烯/α-烯烃共聚物(例如三井石油化学株式会社(Mitsui Petrochemicals CompanyLimited)的和埃克森化学公司(Exxon Chemical Company)的)、均质支化、实质上线性乙烯/α-烯烃聚合物(例如可购自陶氏化学公司的和聚乙烯)以及乙烯嵌段共聚物(例如可购自陶氏化学公司的聚乙烯)。实质上线性乙烯共聚物描述在USP 5,272,236、5,278,272以及5,986,028中。
电压稳定剂
除聚合组分以外，聚合组合物还包括电压稳定剂(或VSA)。如本文所用，“电压稳定剂”是当暴露于电场时降低对聚合材料的损坏的化合物。已认为VSA可截获或钝化电子以抑制绝缘材料中的电树枝生长或者以提供高局域场(附近缺陷或污染物)的有效屏蔽以由此减少可给予聚烯烃损坏的注入电子的能量和/或频率。将VSA与聚合组分掺合抑制或者延迟树枝生长。不受特定理论束缚，相信VSA填充和/或包围聚合组分中的缺陷，缺陷是树起始的点。缺陷包括存在于聚合组分中的空隙和/或杂质。
VSA是选自具有以下结构的化合物中的一者或多者的三嗪：
a)在一个实施例中，聚合组合物含有约0.1wt％或约0.2wt％到约5wt％，或约3wt％，或约1wt％VSA。
b)在一个实施例中，VSA可为结构(I)到(III)的两种或三种不同三嗪的混合物。
c)上述VSA出乎意料地改进含有本发明聚合组合物的绝缘层的直流电(“DC”)击穿强度。DC击穿强度的改进可见于下文描述的实例1-3中展示的增加DC击穿强度中。
此外，本发明VSA展示在聚烯烃基质中的良好溶解度和低迁移趋势。本发明VSA可与聚合组合物的其它组分，尤其是交联剂一起有效利用。
在各种实施例中，含有以上VSA中的一者或多者的聚合组合物的DC击穿强度可为至少400kV/mm，至少425kV/mm，或至少4.50kV/mm，和至多700kV/mm，6.50kV/mm，600kV/mm，或550kV/mm。DC击穿强度根据以下测试方法部分中所提供的程序测定。在一个实施例中，聚合组合物的DC击穿强度可在467kV/mm到.543kV/mm范围内。
在一个实施例中，含有以上VSA中的一者或多者的聚合组合物的DC击穿强度可比具有相同组成但缺乏VSA的比较聚合组合物大至少5％，至少10％，至少15％，或至少20％。在一个实施例中，含有以上VSA中的一者或多者的聚合组合物的DC击穿强度可在比具有相同组成但缺乏VSA的比较聚合组合物大10％到40％，或13％到32％范围内。
添加剂
上述聚合组合物中的任何可任选地含有一种或多种添加剂。适合添加剂的非限制性实例包括抗氧化剂、稳定剂、加工助剂、防焦剂和/或交联辅助剂。作为抗氧化剂，可提及位阻或半受阻酚、芳香族胺、脂肪族位阻胺、有机亚磷酸盐、硫代化合物以及其混合物。典型交联辅助剂可包括具有乙烯基或烯丙基的化合物，例如三聚氰酸三烯丙酯、异氰脲酸三烯丙酯以及二丙烯酸酯、三丙烯酸酯或四丙烯酸酯。作为其它添加剂，可提及阻燃添加剂、除酸剂、无机填充剂、抗水-树剂以及其它电压稳定剂。
如本文所用，“防焦剂”是在挤压聚合组合物期间在所用典型挤压温度下，在与无所述化合物的经挤压的相同聚合组合物相比时减少焦化形成的化合物。除防焦特性之外，防焦剂可同时产生其它效果，如增强，即在交联步骤期间增强交联性能。
聚合组合物可包含本文公开的两个或更多个实施例。
经涂布导体
本发明提供含有本发明聚合组合物的物件。在一个实施例中，物件包括导体和导体上的涂层。这形成经涂布导体。导体可为单个电缆或粘结在一起的多个电缆(即电缆芯或芯)。经涂布导体可为柔性、半刚性或刚性的。适合的经涂布导体的非限制性实例包括柔性布线(如用于消费电子产品的柔性布线)、电力电缆、用于蜂窝电话和/或计算机的充电器电线、计算机数据线、电源线、器具布线材料以及消费电子辅线。
涂层位于导体上。涂层可为一个或多个内层，如绝缘层和/或屏蔽层和/或半导体层。涂层还可包括一个或多个外层(还称为“夹套”或“护套”)。涂层包括如本文所公开的本发明聚合组合物中的任何。如本文所用，“在……上”包括涂层(或层)与导体之间的直接接触或间接接触。“直接接触”是从而涂层立即接触导体，其中无介入层和/或无介入材料位于涂层与导体之间的配置。“间接接触”是从而介入层和/或介入结构或材料位于导体与涂层之间的配置。涂层可完全或部分覆盖或者围绕或包裹导体。涂层可为围绕导体的唯一组件。或者，涂层可为包裹金属导体的多层结构、夹套或护套的一个层。
在一个实施例中，提供经涂布导体并且其包括导体、内层以及最外不透明层(或护套)。最外不透明层是暴露层或与周围环境接触的层。内层位于导体与最外层之间。换句话说，内层不暴露于周围环境，和/或不暴露于日光。内层包括如以上所公开含有聚烯烃和VSA的聚合组合物。VSA可为结构(I)、(II)、(III)的任何三嗪，或如本文所公开的两种不同三嗪的掺合物。
在一个实施例中，内层(含有聚烯烃和VSA)不包括暴露于日光的层。
在一个实施例中，内层的聚合组合物含有聚乙烯。
在一个实施例中，内层的聚合组合物含有交联聚乙烯。
在一个实施例中，经涂布导体是在高于1kV，或高于6kV到36kV(中压)或高于36kV(高压)，或高于220kV(超高压)的电压下操作的电力电缆。图1显示绝缘电力电缆10(即，经涂布导体)，其包括金属导体12，内部屏蔽层14，绝缘层16，外部屏蔽层18，绕线或导电带的金属网20，以及最外层22(也称为护套)。最外层22不透明。
在一个实施例中，内部屏蔽层14和/或绝缘层16和/或外部屏蔽层18由含有聚乙烯和结构(I)、(II)和/或(III)的三嗪的聚合组合物组成。换句话说，内层可为绝缘层和/或屏蔽层，其中的一者或两者含有本发明聚合组合物。
本发明经涂布导体可包含本文公开的两个或更多个实施例。
定义
本文中对元素周期表的所有提及应指的是由CRC出版公司(CRC Press，Inc.)2003年出版并且版权所有的元素周期表。另外，对一个或多个族的任何提及应是使用IUPAC系统给族编号的在这一元素周期表中反映的一个或多个族。除非相反地陈述、由上下文暗示或在本领域中惯用，否则所有份数和百分比都以重量计。出于美国专利实务的目的，本文中所提及的任何专利、专利申请或公开的内容都在此以全文引用的方式并入(或其等效美国版本如此以引用的方式并入)，尤其在所属领域中的合成技术、定义(在并未与本文提供的任何定义不一致的程度上)和常识的公开内容方面。
本文中所列举的任何数值范围包括从下限值到上限值以一个单位递增的所有值，其限制条件是在任何下限值与任何较高值之间存在至少2个单位的间隔。举例来说，如果陈述组分的量或组成特性或物理特性的值(如掺合物组分的量、软化温度、熔融指数等)在1和100之间，那么这意味着所有个别值(如1、2、3等)和所有子范围(如1到20、55到70、197到100等)都明确列举在本说明书中。对于小于1的值，一个单位按需要被视为0.0001、0.001、0.01或0.1。这些仅是特别预期的实例，并且所列举的最低值和最高值之间数值的所有可能组合将被视为明确陈述在本申请中。换句话说，本文中所列举的任何数值范围包括在所陈述的范围内的任何值或子范围。如本文中所论述，已列举数值范围，参考熔融指数、熔体流动速率以及其它特性。
如本文所用，术语“掺合物”或“聚合物掺合物”是两种或更多种聚合物的掺合物。这种掺合物可能是或可能不是可混溶的(在分子水平不相分离)。这种掺合物可能是或可能不是相分离的。这种掺合物可能含有或可能不含有一种或多种畴构型，如由透射电子光谱法、光散射、x射线散射以及所属领域中已知的其它方法所测定。
绝缘体的“DC击穿强度”是致使一部分绝缘体变得导电的最低电压，其根据以下测试方法部分中所提供的程序测量。
“电缆”和类似术语是保护性绝缘材料、夹套或护套内的至少一个电线或光纤。典型地，电缆是典型地在常见保护性绝缘材料、夹套或护套中粘结在一起的两个或更多个电线或光纤。夹套内的个别电线或纤维可为裸露的、经覆盖的或被隔离的。组合电缆可含有电线和光纤两者。电缆等可经设计用于低压、中压以及高压应用。典型电缆设计说明于USP 5,246,783、6,496,629以及6,714,707中。
“组合物”和类似术语意指两种或更多种组分的混合物或掺合物。如本文所用，术语“组合物”包括构成所述组合物的材料的混合物以及由所述组合物的材料形成的反应产物和分解产物。
术语“包含”和其派生词并不意图排除任何额外组分、步骤或程序的存在，无论其是否在本文中公开。为了避免任何疑问，除非相反地陈述，否则在本文中通过使用术语“包含”所要求的的所有组合物可包括无论聚合或呈其它方式的任何其它添加剂、佐剂或化合物。相反，术语“主要由……组成”从任何随后列举的范围排除任何其它组分、步骤或程序，除了对可操作性来说不是必不可少的那些之外。术语“由……组成”排除未具体界定或列举的任何组分、步骤或程序。除非另外说明，否则术语“或”是指单独以及以任何组合形式列举的成员。
“导体”是用于在任何电压(DC、AC或暂态)下传递能量的细长形状的元件(电线、电缆、纤维)。导体典型地是至少一个金属线或至少一个金属电缆(如铝或铜)但可包括光纤。
“交联”、“固化”以及类似术语意思指聚合物在成形为物件之前或之后经受或暴露于诱导交联的处理并且二甲苯或十氢萘(decalene)可萃取物小于或等于90重量％(即，大于或等于10重量％凝胶含量)。
“绝缘层”是体积电阻率大于1010ohm-cm，或大于1012ohm-cm的层。
如本文所用，“层”是围绕导体的聚合物类层，例如电绝缘层、半导体层、护套、保护层、阻水层或执行组合功能的层(例如装有导电填充剂的保护层)。
术语“中压”一般意思指在6kV与约36kV之间的电压，而“高压”意思指高于36kV的电压，并且“超高压”一般意思指大于220kV的电压。所属领域的技术人员理解在美国外这些一般电压范围可能不同。
如本文所用，术语“不透明”是阻断至少自然光(即，日光)的材料。换句话说，对于波长是约250nm到约800nm的光能，不透明材料是不能透过的。
术语“聚合物”是通过聚合相同或不同类型的单体制备的大分子化合物。“聚合物”包括均聚物、共聚物、三元共聚物、互聚物等。术语“互聚物”是通过至少两种类型的单体或共聚单体的聚合制备的聚合物。其包括(但不限于)共聚物(这通常是指由两种不同类型的单体或共聚单体制备的聚合物)、三元共聚物(这通常是指由三种不同类型的单体或共聚单体制备的聚合物)、四元共聚物(这通常是指由四种不同类型的单体或共聚单体制备的聚合物)等等。
“屏蔽层”可为半导体或电阻型。具有半导体特性的屏蔽层的体积电阻率值当在90℃下测量时是小于1000Ω-m或小于500Ω-m。具有电阻特性的屏蔽层的体积电阻率值大于半导体层。具有电阻特性的屏蔽层的介电常数典型地大于约10。
测试方法
DC击穿强度测量
使用利用圆形0.25”探针和较大平坦铜板的设备进行DC击穿强度测量。对于每个测试，以300V/s的速率升高电压直到检测到击穿。“击穿”定义为其中通过电源读取的电压突然下降到设定值的10％以下的点。相较于电流尖峰测量选择这种方法以消除来自静态放电的错误肯定。从ASTM D3755(针对DC测试)考虑，这种DC击穿测试程序与ASTM D149(针对AC测试)极类似。DC击穿强度是样品未能针对厚度标准化的电压。ASTM方法建议每个样品五个测量值以用于足够标准差；然而，在此较早测试揭露标准差不达到水平直到约十次测试，而标准误差继续进一步下降。作为标准误差与时间之间的折中，针对每个样品进行十次测量并且提供平均值作为材料的DC击穿强度。
实例
样品制备
首先将含有某些量的添加剂的PE树脂干掺合，并且然后在约200RPM的速度下于微型18mm双螺杆挤压机上熔融掺合混合物。生产量是7lb/h，熔融温度是约180-200℃。将经挤压线料空气冷却并且切成球粒。
通过使用单螺杆挤压机制造含有某些量的添加剂的PE膜。沿着挤压机在170-210℃范围内的温度下铸造膜。模口间隙设定为4mm并且冷却辊温度是40℃。膜厚度是约1-2密耳。
实例1-3和比较样品A-C
实例1是含有1wt％以下三嗪电压稳定剂的LDPE，其是于1-甲氧基-2-丙醇中的85wt％溶液：
其可以商品名TINUVINTM 400购自巴斯夫(BASF)。在这个实例中使用的LDPE是来自美国密歇根州米德兰(Midland，MI，USA)陶氏化学公司的LDPE DXM446。
实例2是含有1wt％以下三嗪电压稳定剂的LDPE：
其可以商品名TINUVINTM 405购自巴斯夫。在这个实例中使用的LDPE与实例1中所描述相同。
实例3是含有0.85wt％在实例2中使用的相同电压稳定剂的LDPE。在这个实例中使用的LDPE与实例1中所描述相同。
实例4是含有1wt％以下三嗪电压稳定剂的LDPE：
其可以商品名TINUVINTM 479购自巴斯夫。在这个实例中使用的LDPE与实例1中所描述相同。
比较样品A是无电压稳定剂的LDPE。在比较样品A中使用的LDPE与实例1中所描述相同。
比较样品B是含有1wt％CYASORBTM UV 1164的LDPE，其具有以下结构：
在比较样品B中使用的LDPE与实例1中所描述相同。
比较样品C是含有1wt％CHIMASSORBTM 944(具有以下结构的受阻胺稳定剂)的LDPE：
在比较样品C中使用的LDPE与实例1中所描述相同。
根据上文所描述的程序针对DC击穿强度分析实例1-3和比较样品A-C。结果提供在以下表1中：
表1-击穿强度分析
| 样品 | 添加剂名称 | 平均DC击穿强度，(KV/mm) | 击穿强度改进％ |
| 比较样品A | 无 | 412.381 | - |
| 比较样品B | CYASORBTM UV1164 | 369.303 | -10.4 |
| 比较样品C | CHIMASSORBTM 944 | 374.199 | -9.3 |
| 实例1 | TINUVINTM 400 | 495.295 | 20.1 |
| 实例2 | TINUVINTM 405 | 467.058 | 13.3 |
| 实例3 | 0.85％TINUVINTM 405 | 507 | 22.9 |
| 实例4 | TINUVINTM 479 | 542.3 | 31.5 |
击穿强度结果指示与其它三嗪结构，如CYASORBTM UV 1164和CHIMASSORBTM 944相比，特定/独特三嗪类型结构TINUVINTM 400、405以及479提供显著DC电压稳定性能。
尤其期望的是，本发明不限于本文中所含有的实施例和说明，而是包括那些实施例的修改形式，所述修改形式包括在所附权利要求书范围内出现的实施例的部分和不同实施例的要素的组合。
Claims (10)
1.一种经涂布导体，其包含：
导体；
最外不透明层；
位于所述导体与所述最外层之间的内层，所述内层包含聚合组合物，所述聚合组合物包含：
聚烯烃；和
三嗪，其选自由具有结构(I)、(II)或(III)中的一个的化合物和其两者或更多者的组合组成的群组：
(I)
(II)
(III)
2.根据权利要求1所述的经涂布导体，其中所述聚烯烃是聚乙烯。
3.根据权利要求1所述的经涂布导体，其中所述聚合组合物与所述导体直接接触。
4.根据权利要求1到3中任一权利要求所述的经涂布导体，其中所述三嗪由具有结构(I)的化合物组成。
5.根据权利要求1到3中任一权利要求所述的经涂布导体，其中所述三嗪由具有结构(II)的化合物组成。
6.根据权利要求1到3中任一权利要求所述的经涂布导体，其中所述三嗪由具有结构(III)的化合物组成。
7.根据权利要求1到3中任一权利要求所述的经涂布导体，其中所述聚合组合物包含0.1wt％到5wt％所述三嗪。
8.根据权利要求1到3中任一权利要求所述的经涂布导体，其中所述经涂布导体选自由中压电力电缆、高压电力电缆以及超高压电力电缆组成的群组。
9.根据权利要求1到3中任一权利要求所述的经涂布导体，其中所述内层是绝缘层。
10.根据权利要求1到3中任一权利要求所述的经涂布导体，其中所述内层是屏蔽层。
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Also Published As
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|---|---|
| CA2908972A1 (en) | 2014-10-23 |
| CN105209534A (zh) | 2015-12-30 |
| MX2015014642A (es) | 2016-03-01 |
| US20160027550A1 (en) | 2016-01-28 |
| EP3643741B1 (en) | 2023-07-05 |
| EP2986668A1 (en) | 2016-02-24 |
| EP3643741A1 (en) | 2020-04-29 |
| WO2014172107A1 (en) | 2014-10-23 |
| EP3395874A3 (en) | 2018-11-28 |
| US10490318B2 (en) | 2019-11-26 |
| JP2016520960A (ja) | 2016-07-14 |
| EP3395874B1 (en) | 2020-03-11 |
| KR102181765B1 (ko) | 2020-11-24 |
| KR20150143487A (ko) | 2015-12-23 |
| CA2908972C (en) | 2022-08-02 |
| TW201500183A (zh) | 2015-01-01 |
| JP6348973B2 (ja) | 2018-06-27 |
| MX2020007324A (es) | 2020-09-07 |
| EP3395874A2 (en) | 2018-10-31 |
| EP2986668B1 (en) | 2018-07-18 |
| BR112015021505A2 (pt) | 2017-07-18 |
| TWI613072B (zh) | 2018-02-01 |
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