CN114008128A - 膨胀低密度聚乙烯绝缘物组合物 - Google Patents
膨胀低密度聚乙烯绝缘物组合物 Download PDFInfo
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- CN114008128A CN114008128A CN201980097916.4A CN201980097916A CN114008128A CN 114008128 A CN114008128 A CN 114008128A CN 201980097916 A CN201980097916 A CN 201980097916A CN 114008128 A CN114008128 A CN 114008128A
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- expanded
- density polyethylene
- expanded polymeric
- polymeric coating
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- 239000005977 Ethylene Substances 0.000 description 1
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- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
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- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
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- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
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- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
一种电缆包含:(a)导体;以及(b)围绕所述导体的至少一部分的膨胀聚合物涂料,所述膨胀聚合物涂料包含:(i)70.0wt.%到99.8wt.%的低密度聚乙烯均聚物;以及(ii)0.2wt.%到5.0wt.%的膨胀聚合物微球,所述膨胀聚合物微球的D50平均直径为25μm到40μm,其中所述膨胀聚合物涂料的密度为0.75g/cc或更小。
Description
技术领域
本发明总体上涉及低密度聚乙烯绝缘物组合物,并且更具体地,涉及包括围绕导体的膨胀低密度聚乙烯绝缘物的导电电缆。
背景技术
高频信号在电缆内的传输速度很重要。高频信号通过电缆的传输速度受存在于电缆的导体表面上的任何绝缘物材料的介电常数的影响。电缆的导体表面上的绝缘物的介电常数越低,信号通过电缆的速度就越高。
常规实心绝缘物通常包含氟化乙烯/丙烯共混物和聚四氟乙烯,并且表现出2.10或更高的介电常数。膨胀绝缘物使实现低于2.10的介电常数成为可能,但是膨胀绝缘物的微结构中的空隙需要均匀地分散以实现这样的介电常数。膨胀绝缘物是通过物理发泡或化学发泡形成的,并且通常包含高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)和成核剂。物理发泡依赖于如气体等起泡剂和成核剂来实现充分一致的发泡。化学发泡依赖于添加剂在绝缘物中的分解或反应来产生引起发泡的气体。
最近,已在物理发泡过程中利用了膨胀性微球。通常,单独的膨胀性微球不能使绝缘物充分发泡或不能提供绝缘物的均匀发泡。因此,使用了起泡剂与膨胀性微球的组合来获得所期望的发泡性能。WO2018049555利用膨胀性微球,但仅用作物理发泡起泡剂的成核剂。例如,WO2018049555公开了具体地使用至多1.6wt.%膨胀性微球作为成核剂与氟树脂结合。EP1275688B1解释了单独的热膨胀性微球不能使膨胀绝缘物稳定,并且在膨胀时不能提供均匀大小的孔。EP1275688B1进一步解释了在小于9重量份的浓度下,膨胀性微球的膨胀不充分。因此,除了膨胀性微球之外,EP1275688B1还利用化学发泡剂来提供足够的发泡。
因此,令人惊奇的是提供一种包括膨胀绝缘物的电缆,所述膨胀绝缘物可以在不需要额外的化学或物理起泡剂的情况下使用膨胀性微球实现低于2.10的介电常数。
发明内容
本发明提供了一种包括膨胀绝缘物的电缆,所述膨胀绝缘物表现出在不需要额外的化学或物理起泡剂的情况下使用膨胀性微球低于2.10的介电常数。
本发明是以下发现的结果:膨胀绝缘物的树脂的密度和熔体强度影响膨胀性微球的膨胀,这进而会影响所得膨胀绝缘物的介电常数。对所述膨胀绝缘物使用树脂,按所述膨胀绝缘物重量计,所述树脂包括大于70wt.%的低密度聚乙烯(LDPE),所述膨胀性微球更均匀地分散在所述树脂中并且如与小于70wt.%的膨胀绝缘物为LDPE的所述膨胀绝缘物相比,表现出更大膨胀。
本发明可具体用于引线和电缆导体绝缘物。
根据本发明的第一方面,一种电缆包括:
(a)导体;以及
(b)围绕所述导体的至少一部分的膨胀聚合物涂料,所述膨胀聚合物涂料包括:
(i)70.0wt.%到99.8wt.%的低密度聚乙烯均聚物;以及
(ii)0.2wt.%到5wt.%的膨胀聚合物微球,所述膨胀聚合物微球的D50平均直径为25μm到40μm,其中所述膨胀聚合物涂料的密度为0.75g/cc或更小。
根据本发明的第二方面,一种母料组合物包含:
(a)70.0wt.%到99.8wt.%的低密度聚乙烯均聚物;
(b)0.5wt.%到30wt.%的膨胀聚合物微球;以及
(c)0wt.%到25wt.%的线性低密度聚乙烯,其中所述母料组合物不含高密度聚乙烯、橡胶、偶氮二甲酰胺和氟树脂。
具体实施方式
如本文所用,术语“和/或”当用于两个或更多个项目的列表中时,意指所列项目中的任一个可单独使用,或可使用所列项目中的两个或更多个的任何组合。例如,如果将组合物描述为含有组分A、B和/或C,则组合物可以仅含有A;仅含有B;仅含有C;含有A与B的组合;含有A与C的组合;含有B与C的组合;或含有A、B及C的组合。
所有范围包含端点,除非另有说明。聚合物式中的下标值是指聚合物的指定组分的每分子单元的摩尔平均数。
测试方法是指截至本文件优先权日的最新测试方法,除非日期用测试方法编号表示为带连字符的两位数。对试验方法的引用包括对试验协会和试验方法编号的引用。测试方法组织通过以下缩写之一引用:ASTM是指ASTM国际(以前称为美国材料与试验协会(American Society for Testing and Materials));EN是指欧洲规范(European Norm);DIN是指德国标准化学会(Deutsches Institut für Normung);而ISO是指国际标准化组织(International Organization for Standards)。
如本文所用,术语“不含”是指按被表述为“不含”成分的物质的重量计,特定成分或所述成分的反应产物小于0.001重量百分比(wt.%)。
电缆
本公开的电缆包含导体,所述导体具有围绕所述导体的至少一部分的膨胀聚合物涂料。所述电缆可以包括位于所述导体与所述膨胀聚合物涂料之间的内护套。所述内护套可以包括如下更详细描述的线性低密度聚乙烯。包括线性低密度聚乙烯的内护套的并入在增加电缆的机械耐久性方面可能是有利的。此外,外护套可以围绕所述膨胀聚合物涂料的至少一部分。所述外护套可以包括如下更详细描述的高密度聚乙烯。包括高密度聚乙烯的外护套的并入在增加电缆的机械耐久性方面可能是有利的。所述电缆可以包含多于一个导体。所述导体可以是延伸所述电缆的长度的实心组件。所述导体可以具有圆形横截面形状。所述导体可以在电缆的端部处与一个或多个连接器电耦接。所述导体可以包括如铜、银、金和铂等一种或多种金属。在包含多于一个导体的电缆的实例中,每个导体可以具有膨胀聚合物涂料。任选地,所述电缆可以包含一个或多个额外的层或护套,所述额外的层或护套包括聚合材料和/或金属。所述导体是被配置成传输一个或多个电信号的电导体。所述电缆可特别用作小形状因子可插拔数据电缆。
聚合物涂料
膨胀聚合物涂料围绕导体的至少一部分。可以使膨胀聚合物涂料与导体直接接触。可以通过内护套使膨胀聚合物涂料与导体部分或完全脱离直接接触。在电缆的一部分或基本上整个电缆中,膨胀聚合物涂料可以不含空隙。膨胀聚合物涂料包括低密度聚乙烯均聚物(LDPE)。LDPE的密度的范围为0.915克每立方厘米(g/cc)到0.925g/cc。本文所提供的聚合物和聚合物涂料密度是根据ASTM方法D792确定的。LDPE的多分散性指数(“PDI”)可以在1.0到30.0的范围内或在2.0到15.0的范围内,如通过凝胶渗透色谱法测量的。适用于膨胀聚合物涂料的LDPE的熔融指数(I2)可以为0.1克/10分钟到20克/10分钟。本文所提供的熔融指数是根据ASTM方法D1238确定的。除非另外指出,否则熔融指数是在190℃和2.16Kg下确定的。LDPE树脂是本领域已知的,可商购获得的并且通过包含但不限于溶液相、气相或淤浆相和齐格勒-纳塔(Ziegler-Natta)、茂金属或受限几何催化(CGC)的方法制备。可商购获得的LDPE的一个实例包含可从陶氏化学公司(The Dow Chemical Company)获得的AXELERONTM CX-1258 NT LDPE化合物。
膨胀聚合物涂料包括所述膨胀聚合物涂料的70wt.%到99.8wt.%的LDPE。所述膨胀聚合物涂料可以包括所述膨胀聚合物涂料的70wt.%或更大、或71wt.%或更大、或72wt.%或更大、或73wt.%或更大、或74wt.%或更大、或75wt.%或更大、或76wt.%或更大、或77wt.%或更大、或78wt.%或更大、或79wt.%或更大、或80wt.%或更大、或81wt.%或更大、或82wt.%或更大、或83wt.%或更大、或84wt.%或更大、或85wt.%或更大、或86wt.%或更大、或87wt.%或更大、或88wt.%或更大、或89wt.%或更大、或90wt.%或更大、或91wt.%或更大、或92wt.%或更大、或93wt.%或更大、或94wt.%或更大、或95wt.%或更大、或96wt.%或更大、或97wt.%或更大、或98wt.%或更大、或99wt.%或更大、或99.8wt.%或更大,而同时,99.8wt.%或更小、或99wt.%或更小、或98wt.%或更小、或97wt.%或更小、或96wt.%或更小、或95wt.%或更小、或94wt.%或更小、或93wt.%或更小、或92wt.%或更小、或91wt.%或更小、或90wt.%或更小、或89wt.%或更小、或88wt.%或更小、或87wt.%或更小、或86wt.%或更小、或85wt.%或更小、或84wt.%或更小、或83wt.%或更小、或82wt.%或更小、或81wt.%或更小、或80wt.%或更小、或79wt.%或更小、或78wt.%或更小、或77wt.%或更小、或76wt.%或更小、或75wt.%或更小、或74wt.%或更小、或73wt.%或更小、或72wt.%或更小、或71wt.%或更小或更小。
所述膨胀聚合物涂料可以包括线性低密度聚乙烯均聚物(LLDPE)。适用于本文的LLDPE的密度可以在0.918g/cc到0.935g/cc的范围内。适用于本文的LLDPE的熔融指数I2可以为0.1克/10分钟到20克/10分钟适用于本文的LLDPE的重均分子量(“Mw”)可以为100,000g/mol到130,000g/mol(如通过凝胶渗透色谱法测量的)。此外,适用于本文的LLDPE的数均分子量(“Mn”)可以为5,000g/mol到8,000g/mol。因此,在各个实施例中,LLDPE的分子量分布(Mw/Mn,或多分散性指数(“PDI”))可以为12.5到26。用于制备LLDPE的方法是本领域通常已知的,并且可以包含使用齐格勒或飞利浦催化剂,并且聚合可以在溶液或气相反应器中执行。适合的可商购的LLDPE的实例包含可从陶氏化学公司获得的AXELERONTMCS-7540NTLLDPE。
膨胀聚合物涂料包括所述膨胀聚合物涂料的0wt.%到25wt.%的LLDPE。所述LLDPE可以占所述膨胀聚合物涂料的0wt.%或更大、1wt.%或更大、2wt.%或更大、3wt.%或更大、4wt.%或更大、5wt.%或更大、或6wt.%或更大、或7wt.%或更大、或8wt.%或更大、或9wt.%或更大、或10wt.%或更大、或11wt.%或更大、或12wt.%或更大、或13wt.%或更大、或14wt.%或更大、或15wt.%或更大、或16wt.%或更大、或17wt.%或更大、或18wt.%或更大、或19wt.%或更大、或20wt.%或更大、或21wt.%或更大、或22wt.%或更大、或23wt.%或更大、或24wt.%或更大、或25wt.%或更大,而同时,25wt.%或更小、或24wt.%或更小、或23wt.%或更小、或22wt.%或更小、或21wt.%或更小、或20wt.%或更小、或19wt.%或更小、或18wt.%或更小、或17wt.%或更小、或16wt.%或更小、或15wt.%或更小、或14wt.%或更小、或13wt.%或更小、或12wt.%或更小、或11wt.%或更小、或10wt.%或更小、或9wt.%或更小、或8wt.%或更小、或7wt.%或更小、或6wt.%或更小、或5wt.%或更小、或4wt.%或更小、或3wt.%或更小、或2wt.%或更小、或1wt.%或更小。
所述膨胀聚合物涂料可以不含选自由以下组成的组的多于一种组分之一或任何组合:高密度聚乙烯(HDPE)、橡胶、偶氮二甲酰胺和氟树脂。如本文所用,HDPE是密度为0.94g/cc到0.98g/cc的基于乙烯的聚合物。HDPE的熔融指数I2为0.1克/10分钟到25克/10分钟。HDPE的非限制性实例包含可从陶氏化学公司获得的AXELERONTMCX-6944NT HDPE化合物。如本文所用,术语氟树脂涵盖含氟聚合物。示例性氟树脂包含聚四氟乙烯。如本文所用,术语“橡胶”涵盖二烯单体的聚合物或共聚物。
所述膨胀聚合物涂料可以包括一种或多种抗氧化剂。抗氧化剂的实例包含但不限于受阻酚,如四[亚甲基(3,5-二叔丁基-4-羟基氢化-肉桂酸)]甲烷;双[(β-(3,5-二叔丁基-4-羟基苄基)甲基羧乙基)]-硫化物;4,4'-硫双(2-甲基-6-叔丁基酚);4,4'-硫双(2-叔丁基-5-甲基酚);2,2'-硫双(4-甲基-6-叔丁基酚);和硫代二亚乙基双(3,5-二叔丁基-4-羟基)氢化肉桂酸酯;亚磷酸酯和亚膦酸酯,如三(2,4-二叔丁基苯基)亚磷酸酯和二-叔丁基苯基亚膦酸酯;硫代化合物,如硫代二丙酸二月桂酯、硫代二丙酸二肉豆蔻酯和硫代二丙酸二硬脂酯;各种硅氧烷;聚合的2,2,4-三甲基-1,2-二氢喹啉;n,n'-双(1,4-二甲基戊基-对苯二胺);烷基化二苯胺;4,4'-双(α,α-二甲基苯甲基)二苯胺;二苯基-对苯二胺、混合的二芳基对苯二胺和其它受阻胺抗降解剂或稳定剂。按膨胀聚合物涂料的重量计,抗氧化剂可以以例如0.01wt.%到5wt.%、或0.01wt.%到0.1wt.%或0.01wt.%到0.3wt.%的量使用。
膨胀性微球
膨胀聚合物涂料包括膨胀聚合物微球。膨胀微球是膨胀性聚合物微球从未膨胀微球转变为膨胀微球的结果。随着膨胀性微球经历转变,聚合物涂料从未膨胀聚合物涂料转变为膨胀聚合物涂料。膨胀性聚合物微球在暴露于热时从未膨胀状态膨胀到膨胀状态。膨胀性微球是单孔颗粒,其包括包封挥发性流体的热塑性聚合物的外壳。在加热时,所述外壳的热塑性聚合物软化,并且挥发性材料膨胀,从而使微球的大小增加。冷却时,外壳中的热塑性聚合物硬化并保持其扩大的尺寸,并且保留在微球内的气态挥发性流体会冷凝,从而导致微球中的气压低于101.325kPa。
热塑性聚合物外壳可以包括甲基丙烯酸甲酯、丙烯腈、偏二氯乙烯、邻氯苯乙烯、对叔丁基苯乙烯、乙酸乙烯酯和/或其共聚物。外壳内部的挥发性流体可以包括脂肪族烃气体,如异丁烯、戊烷或异辛烷。膨胀性聚合物微球表现出在范围为以下的温度下从未膨胀状态膨胀到膨胀状态:80℃或更高、或90℃或更高、或100℃或更高、或110℃或更高、或120℃或更高、或130℃或更高、或140℃或更高、或150℃或更高、或160℃或更高、或170℃或更高、或180℃或更高、或190℃或更高、或200℃或更高、或210℃或更高、或220℃或更高、或230℃或更高、或240℃更大,而同时,250℃或更低、或240℃或更低、或230℃或更低、或220℃或更低、或210℃或更低、或200℃或更低、或190℃或更低、或180℃或更低、或170℃或更低、或160℃或更低、或150℃或更低、或140℃或更低、或130℃或更低、或120℃或更低、或110℃或更低、或100℃或更低、或90℃或更低。膨胀性微球体表现出膨胀性微球中的一些膨胀微球体开始从未膨胀状态转变为膨胀状态的起始温度。膨胀性微球表现出95%或更多的膨胀性微球从未膨胀状态转变为膨胀状态的最大温度。如本文所用,“低温度微球”的起始温度为130℃到145℃。如本文所用,“高温度微球”的起始温度为155℃到175℃。膨胀性聚合物微球例如可从诺力昂公司(Nouryon)以商标EXPANCELTM商购获得。所述微球通常是球形形状的颗粒,但可以采用各种形状,如管、椭圆体、立方体、颗粒等,当暴露于热能时,所有这些都适于膨胀。膨胀性微球的D50平均直径或最长线性尺寸为25μm到40μm或28μm 38μm,如通过在Malvern Mastersizer Hydro 2000SM设备上对湿样品进行的激光散射所测量的。平均直径或最长线性尺寸呈现为D50体积中值直径。例如,膨胀性微球的平均直径或最长线性尺寸为25μm或更大、或26μm或更大、或27μm或更大、或28μm或更大、或29μm或更大、或30μm或更大、或31μm或更大、或32μm或更大、或33μm或更大、或34μm或更大、或35μm或更大、或36μm或更大、或37μm或更大、或38μm或更大、或39μm或更大,而同时,40μm或更小、或39μm或更小、或38μm或更小、或37μm或更小、或36μm或更小、或35μm或更小、或34μm或更小、或33μm或更小、或32μm或更小、或31μm或更小、或30μm或更小、或29μm或更小、或28μm或更小、或27μm或更小、或26μm或更小。
所述膨胀微球占所述膨胀聚合物涂料的0.2wt.%到5wt.%。所述膨胀微球可以占所述膨胀聚合物涂料的更大的0.2wt.%或0.5wt.%或更大、或1.0wt.%或更大、或1.5wt.%或更大、或2.0wt.%或更大、或2.5wt.%或更大、或3.0wt.%或更大、或3.5wt.%或更大、或4.0wt.%或更大、或4.5wt.%或更大、或5.0wt.%或更大,而同时,5.0wt.%或更小、或4.5wt.%或更小、或4.0wt.%或更小、或3.5wt.%或更小、或3.0wt.%或更小、或2.5wt.%或更小、或2.0wt.%或更小、或1.5wt.%或更小、或1.0wt.%或更小、或0.5wt.%更少。
母料
本发明的聚合物涂料是使用母料形成的。如本文所定义的,术语“母料”是指添加剂在载体树脂中的浓缩混合物。在本发明的上下文中,所述母料包括在包括LDPE的聚烯烃树脂中的膨胀性微球。本发明的母料包括70.0wt.%到99.8wt.%LDPE和0.5wt.%到30wt.%的膨胀性微球。例如,母料可以包括浓度为所述母料的重量的70wt.%或更大、或71wt.%或更大、或72wt.%或更大、或73wt.%或更大、或74wt.%或更大、或75wt.%或更大、或76wt.%或更大、或77wt.%或更大、或78wt.%或更大、或79wt.%或更大、或80wt.%或更大、或81wt.%或更大、或82wt.%或更大、或83wt.%或更大、或84wt.%或更大、或85wt.%或更大、或86wt.%或更大、或87wt.%或更大、或88wt.%或更大、或89wt.%或更大、或90wt.%或更大、或91wt.%或更大、或92wt.%或更大、或93wt.%或更大、或94wt.%或更大、或95wt.%或更大、或96wt.%或更大、或97wt.%或更大、或98wt.%或更大、或99wt.%或更大、或99.8wt.%或更大,而同时,99.8wt.%或更小、或99wt.%或更小、或98wt.%或更小、或97wt.%或更小、或96wt.%或更小、或95wt.%或更小、或94wt.%或更小、或93wt.%或更小、或92wt.%或更小、或91wt.%或更小、或90wt.%或更小、或89wt.%或更小、或88wt.%或更小、或87wt.%或更小、或86wt.%或更小、或85wt.%或更小、或84wt.%或更小、或83wt.%或更小、或82wt.%或更小、或81wt.%或更小、或80wt.%或更小、或79wt.%或更小、或78wt.%或更小、或77wt.%或更小、或76wt.%或更小、或75wt.%或更小、或74wt.%或更小、或73wt.%或更小、或72wt.%或更小、或71wt.%或更小的LDPE。
所述母料可以包括所述母料的重量的0.5wt.%到30.0wt.%的膨胀性微球。例如,所述母料可以包括浓度为所述母料的重量的0.5wt.%或更大、或1wt.%或更大、或2wt.%或更大、或3wt.%或更大、或4wt.%或更大、或5wt.%或更大、或6wt.%或更大、或7wt.%或更大、或8wt.%或更大、或9wt.%或更大、或10wt.%或更大、或11wt.%或更大、或12wt.%或更大、或13wt.%或更大、或14wt.%或更大、或15wt.%或更大、或16wt.%或更大、或17wt.%或更大、或18wt.%或更大、或19wt.%或更大、或20wt.%或更大、或21wt.%或更大、或22wt.%或更大、或23wt.%或更大、或24wt.%或更大、或25wt.%或更大、或26wt.%或更大、或27wt.%或更大、或28wt.%或更大、或29wt.%或更大,同时,30wt.%或更小、或29wt.%或更小、或28wt.%或更小、或27wt.%或更小、或26wt.%或更小、或25wt.%或更小、或24wt.%或更小、或23wt.%或更小、或22wt.%或更小、或21wt.%或更小、或20wt.%或更小、或19wt.%或更小、或18wt.%或更小、或17wt.%或更小、或16wt.%或更小、或15wt.%或更小、或14wt.%或更小、或13wt.%或更小、或12wt.%或更小、或11wt.%或更小、或10wt.%或更小、或9wt.%或更小、或8wt.%或更小、或7wt.%或更小、或6wt.%或更小、或5wt.%或更小、或4wt.%或更小、3wt.%或更小、或2wt.%或更小、或1wt.%或更小的膨胀性微球。
所述母料可以包括所述母料的重量的0wt.%到25wt.%的LLDPE。例如,所述母料可以包括浓度为所述母料的重量的0wt.%或更大、或1wt.%或更大、或2wt.%或更大、或3wt.%或更大、或4wt.%或更大、或5wt.%或更大、或6wt.%或更大、或7wt.%或更大、或8wt.%或更大、或9wt.%或更大、或10wt.%或更大、或11wt.%或更大、或12wt.%或更大、或13wt.%或更大、或14wt.%或更大、或15wt.%或更大、或16wt.%或更大、或17wt.%或更大、或18wt.%或更大、或19wt.%或更大、或20wt.%或更大、或21wt.%或更大、或22wt.%或更大、或23wt.%或更大、或24wt.%或更大,同时25wt.%或更小、或24wt.%或更小、或23wt.%或更小、或22wt.%或更小、或21wt.%或更小、或20wt.%或更小、或19wt.%或更小、或18wt.%或更小、或17wt.%或更小、或16wt.%或更小、或15wt.%或更小、或14wt.%或更小、或13wt.%或更小、或12wt.%或更小、或11wt.%或更小、或10wt.%或更小、或9wt.%或更小、或8wt.%或更小、或7wt.%或更小、或6wt.%或更小、或5wt.%或更小、或4wt.%或更小、3wt.%或更小、或2wt.%或更小、或1wt.%或更小的LLDPE。
所述母料可以包括97wt.%到99.5wt.%的LDPE和0.5wt.%到30.0wt.%的微球。所述母料可以包括0wt.%到25wt.%的LLDPE或者可以包括5wt.%到25wt.%的LLDPE。所述母料可以不含HDPE、橡胶、偶氮二甲酰胺和/或氟树脂。
电缆形成
可以通过在膨胀性微球膨胀之前和/或之后对导体施加母料来形成电缆。在一示例性实施方案中,将母料装入到包括螺杆和头部的挤出机中。将母料与额外的LDPE树脂一起装入到挤出机中。在加热的同时将所述母料与LDPE树脂混合并通过螺杆移动通过挤出机。挤出机内的一个或多个区域,如头部,将母料和LDPE加热到高于膨胀性微球的起始温度的温度。然后将母料和LDPE与导体共挤出,使得母料和LDPE以聚合物涂料的形式围绕导体。暴露于高于起始温度的温度的母料的膨胀性微球可以在挤出机内部以及在围绕导体共挤出之后开始从未膨胀状态转变为膨胀状态。在电缆包含内护套和/或外护套的实例中,导体可以在母料和LDPE挤出之前或之后经历共挤出以形成内护套或外护套。
膨胀聚合物涂料表现出2.10的介电常数,如在2.47千兆赫(GHz)下通过ASTM方法D1531测量的。例如,膨胀聚合物涂料的介电常数可以为2.10或更小,或2.00或更小,或1.90或更小,或1.80或更小,或1.70或更小,或1.60或更小,或1.50或更小,而同时,1.40或更大,或1.50或更大,或1.60或更大,或1.70或更大,或1.80或更大,或1.90或更大,或2.00或更大。
膨胀聚合物涂料表现出2.30或更小的耗散因数,如在2.47GHz下根据ASTM方法D1531测量的。耗散因数是耗散系统中振荡模式的能量损失率的量度。耗散因数可以是2.30或更小,或2.20或更小,或2.10或更小,或2.00或更小,或1.90或更小,或1.80或更小,或1.70或更小,而同时,1.70或更大,或1.80或更大,或1.90或更大,或2.00或更大,或2.10或更大,或2.20或更大,或2.30或更大。
膨胀聚合物涂料的密度为0.75g/cc或更小,如根据ASTM方法D792测量的。例如,膨胀聚合物涂料的密度为0.75g/cc或更小、或0.70g/cc或更小、或0.65g/cc或更小、或0.60g/cc或更小、或0.55g/cc或更小、或0.50g/cc或更小、或0.45g/cc或更小、或0.40g/cc或更小、或0.35g/cc或更小、或0.30g/cc或更小,而同时,0.30g/cc或更大、或0.35g/cc或更大、或0.40g/cc或更大、或0.45g/cc或更大、或0.50g/cc或更大、或0.55g/cc或更大、或0.60g/cc或更大、或0.65g/cc或更大、或0.70g/cc或更大、或0.75g/cc或更大。
出于多种原因,使用膨胀聚合物涂料的70wt.%或更多的LDPE是有利的。首先,与包括HDPE的聚合物涂料相比,LDPE的较低熔体指数允许膨胀性微球在膨胀聚合物涂料中更大的膨胀和更均匀的分布。由于膨胀性微球在膨胀聚合物涂料内膨胀程度和分布更大,因此膨胀聚合物涂料的介电常数低于包括HDPE的可比膨胀聚合物涂料的介电常数。其次,LDPE允许膨胀性微球均匀分布和完全膨胀能力允许从膨胀聚合物涂料中消除偶氮二甲酰胺。如上所解释的,偶氮二甲酰胺和其它常规成核剂的分解可能有害地影响膨胀涂料的介电常数。由于膨胀聚合物涂料的LDPE允许膨胀性微球的均匀分布和完全膨胀,因此可以消除偶氮二甲酰胺。本发明还任选地允许掺入LLDPE作为增强剂。将LLDPE掺入到膨胀聚合物涂料中允许膨胀聚合物涂料的拉伸强度和拉伸伸长率增加。任选地,电缆的膨胀聚合物涂料可以不含氟树脂,如聚四氟乙烯(PTFE)。氟树脂作为电缆的实心绝缘物可在2.47GHz下实现2.10的介电常数,但通常比LDPE费用更高昂。因此,除了在2.47GHz下实现2.10或更低的介电常数之外,消除氟树脂是有利的。
实例
表1列出了用于形成表2和3的本发明实例和比较实例的成分。
表1:
样品制备
通过以下来制备本发明实例和比较实例:将树脂组分(例如,LDPE、LLDPE、HDPE)放置在120℃下的815804BrabenderTM混合器中。以10次旋转每分钟(RPM)的转子速度将组分混合,直至树脂成分熔化为止。将膨胀性微球装入到混合器中以形成混合物。以10RPM将膨胀性微球混合到熔化的树脂中持续2分钟。将混合速度增加到40RPM并且在120℃下混合4分钟。使混合物冷却并切割混合物。
通过以下来制备本发明实例和比较实例的实心薄片:将10g混合物件放置在于120℃下预加热10分钟的100mm×100mm×1mm模具内。通过施加1兆帕(MPa)压力并使压力释放,对每个样品排气8次。在120℃下以10MPa将样品在模具中按压持续5分钟。在10分钟内将模具冷却到23℃,同时维持10MPa的力以形成实心薄片。从模具中移除所述实心薄片。切割所述实心薄片以用于测试样品。
通过以下来使包括膨胀性微球的实心薄片膨胀:在尺寸为195mm×105mm×2mm的模具中,将每个样品放置在0.25mm厚度的聚对苯二甲酸乙二酯片材上。将所述模具加热到175℃并且允许所述膨胀性微球膨胀10分钟。在175℃下在2MPa的压力下对所述模具进行热压缩持续2分钟。将模具上的压力增加到10MPa,同时在10分钟内将模具冷却到23℃。切割所述膨胀薄片以用于测试样品。
表2提供了比较实例(“CE”)A-F和本发明实例(“IE”)1-4的组合物以及相关联的机械性质和电性质。表2和3中提供的wt.%值是相对于其所涉及的具体实例的重量而言的。除非另有说明,否则比较实例和本发明实例的介电常数(“DC”)和耗散因数(“DF”)是根据
ASTM方法D1531测试的,并且密度测试是根据ASTM方法D792执行的。DC和DF测量是在膨胀之前在实例处于实心状态(“实心DC”和“实心DF”)的同时以及在实例膨胀(“膨胀DC”和“膨胀DF”)之后对实例执行的。高温度(“高温”)微球用于包括HDPE的实例中,因为HDPE的熔化温度高于低温度(“低温”)微球的起始温度。提供了在可用的情况下实心状态(微球处于未膨胀状态)和膨胀状态(微球处于膨胀状态)两者的实例的数据。根据ASTM方法D638测量实例的拉伸强度和拉伸伸长率。拉伸强度和拉伸伸长率测量是在膨胀之前在实例处于实心状态(“实心拉伸强度”和“实心拉伸伸长率”)的同时以及在实例中的膨胀性微球膨胀(“膨胀拉伸强度”和“膨胀拉伸伸长率”)之后对实例执行的。
表2:
如可以在表2中看到的,本发明实例1-4的膨胀微球的存在使本发明实例的介电常数从2.29降低到小于2.00。比较实例B表现出2.11的介电常数,这接近目标值2.10。因此,基于其它实例中的趋势,可以安全地得出结论,掺入大于聚合物涂料的0.2wt.%的膨胀性微球将表现出2.10或更小的介电常数。包含聚合物涂料的0.5wt.%和1.0wt.%的膨胀性微球的比较实例E和F分别表现出2.31和2.26的介电常数。比较实例E和F的介电常数与将HDPE掺入到聚合物涂料中限制膨胀性微球的膨胀并且降低微球分散体的均匀性从而导致更高的介电常数的理解一致。如与实心比较实例和膨胀比较实例之间的耗散因数无变化相比,本发明实例1-4的耗散因数表现出膨胀薄片相对于实心薄片降低。
表3提供了比较实例G和H以及本发明实例1和5-8的组合物以及相关联的机械性质和电性质。表3与表2的不同之处在于本发明实例5-8掺入了LLDPE。
表3:
基于常规理解,未知的是掺入LLDPE是否将充分限制聚合物微球的膨胀以最小化或消除由膨胀性微球提供的介电常数益处。同样未知的是将LLDPE添加到掺入了膨胀性微球的聚合物微结构中对机械性能的影响。如本申请的发明人所发现的并且如可以在表3中看到的,在本发明实例5-8中掺入LLDPE并不妨碍膨胀聚合物涂料表现出低于2.10的介电常数。如与具有1.97的膨胀DC并且无LLDPE的本发明实例1相比,本发明实例5-8均表现出2.10或更小的膨胀介电常数。包含LLDPE的本发明实例5-8除了表现出小于2.10的膨胀介电常数之外,还表现出与不具有如本发明实例1等LLDPE的实例相比更大的拉伸强度和拉伸伸长率。因此,与不包含LLDPE的实例相比,本发明实例5-8令人惊讶地表现出低于2.10的介电常数和优异的机械性能两者。
Claims (10)
1.一种电缆,其包括:
(a)导体;以及
(b)围绕所述导体的至少一部分的膨胀聚合物涂料,所述膨胀聚合物涂料包括:
(i)70.0wt.%到99.8wt.%的低密度聚乙烯均聚物;以及
(ii)0.2wt.%到5wt.%的膨胀聚合物微球,所述膨胀聚合物微球的D50平均直径为25μm到40μm,其中所述膨胀聚合物涂料的密度为0.75g/cc或更小。
2.根据权利要求1所述的电缆,其中所述膨胀聚合物微球以所述膨胀聚合物涂料的重量的0.5wt.%到3.0wt.%的浓度存在。
3.根据前述权利要求中任一项所述的电缆,其中所述膨胀聚合物涂料的密度为0.6g/cc或更小。
4.根据前述权利要求中任一项所述的电缆,其中所述膨胀聚合物涂料的密度为0.5g/cc或更小。
5.根据前述权利要求中任一项所述的电缆,其中所述低密度聚乙烯均聚物以所述膨胀聚合物涂料的重量的97.0wt.%到99.5wt.%的浓度存在,并且膨胀聚合物微球以所述膨胀聚合物涂料的重量的0.5wt.%到3.0wt.%的浓度存在,进一步地其中所述膨胀聚合物涂料的密度为0.7g/cc或更小。
6.根据权利要求1到5中任一项所述的电缆,其中所述膨胀聚合物涂料进一步包括:
(iii)线性低密度聚乙烯,所述线性低密度聚乙烯以所述膨胀聚合物涂料的重量的5.0wt.%到25.0wt.%的浓度存在。
7.根据权利要求6所述的电缆,其中所述线性低密度聚乙烯占所述膨胀聚合物涂料的重量的10.0wt.%到20.0wt.%。
8.根据前述权利要求中任一项所述的电缆,其进一步包括:
(c)内护套,所述内护套包括定位在所述导体与所述膨胀聚合物涂料之间的线性低密度聚乙烯;以及
(d)围绕所述膨胀聚合物涂料的外护套,所述外护套包括高密度聚乙烯。
9.根据前述权利要求中任一项所述的电缆,其中所述膨胀聚合物涂料不含高密度聚乙烯、橡胶和氟树脂。
10.一种母料组合物,其包括:
(a)70.0wt.%到99.8wt.%的低密度聚乙烯均聚物;
(b)0.5wt.%到30.0wt.%的膨胀聚合物微球;以及
(c)0wt.%到25.0wt.%的线性低密度聚乙烯,其中所述母料组合物不含高密度聚乙烯、橡胶、偶氮二甲酰胺和氟树脂。
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US20220195232A1 (en) | 2022-06-23 |
KR20220031036A (ko) | 2022-03-11 |
BR112021026461A2 (pt) | 2022-02-08 |
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WO2021000227A1 (en) | 2021-01-07 |
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