CN1195359A - 光纤电缆用的聚丙烯相容的润滑脂组合物 - Google Patents

光纤电缆用的聚丙烯相容的润滑脂组合物 Download PDF

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CN1195359A
CN1195359A CN96196778A CN96196778A CN1195359A CN 1195359 A CN1195359 A CN 1195359A CN 96196778 A CN96196778 A CN 96196778A CN 96196778 A CN96196778 A CN 96196778A CN 1195359 A CN1195359 A CN 1195359A
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composition
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viscotrol
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M·布劳尔
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Caschem Inc
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Caschem Inc
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Abstract

一种用作电缆填充料的润滑脂组合物,此润滑脂组合物含有约25～75重量份的蓖麻油或蓖麻醇酸酯多羟基化合物、约13～71重量份由聚合的蓖麻油或聚异氰酸酯化合物与蓖麻油或蓖麻醇酸酯多羟基化合物的反应产物构成的羟基封端聚合物,和约4～12重量份的胶态粒子诸如煅制氧化硅、沉淀氧化硅、粘土、或它们的混合物。任选地,还可添加赋予其以高温性的抗氧剂组分,赋予其以抗流失性的、一般为橡胶的流失抑止剂,降低其渗水性的超吸收性组分,还可添加微球以减轻制剂的重量,和/或惯用的添加剂诸如杀菌剂、生物杀伤剂等。本发明还涉及制造这样的物件例如电缆的方法,所说的电缆具有围绕处在其中的许多光学纤维的铠装,和一处于其中的本发明的一种润滑脂组合物。

Description

光纤电缆用的聚丙烯相容的润滑脂组合物
                        发明领域
本发明涉及胶态粒子填充的多羟基化合物基组分的润滑脂组合物和其中包括此润滑脂组合物的诸如铠装通讯电缆，特别是那些含光纤集束的物件。
                        发明背景
润滑脂一般为固体或半液体物质，它包括在液体载体中的增稠剂或胶凝剂。几乎所有的具有润滑性的油均可与合适的胶凝剂一起使用以制造润滑脂。石油润滑油、脂油例如蓖麻油、聚亚烷基二醇、合成二酯、硅酮、氟烃和聚苯醚均被发现是工业用的润滑脂(参见，例如，Braithwaite，“Lubrication and lubricants”，Elsevier Publishing Co.，1967，pages 181～183 and 223～228)。胶凝剂频频被用于包括脂肪酸皂、粘土、氧化硅、有机染料、酰胺、和脲衍生物的润滑脂中。胶凝剂形成网络结构，其中载体被毛细管力所固定。
当低应力通过润滑剂试样而施加时，材料的作用基本上像固体。如果所施加的应力高于临界值的话，材料流动而粘度快速地降低。这种粘度降低是非常可逆转的，因为它通常是在填料粒子间网络处破裂而引起的，而这些连接处在消除应力源后能重新形成。
润滑脂的一种想望的性质是缺乏脱水收缩性，即，其保持均匀稠度的能力。一般说来，脱水收缩作用是通过保证在整个组合物中分散合适量的胶凝剂来控制的。
润滑脂组合物已被用于常规的(电)通讯设备和用于光纤电缆两者作为电缆填料。美国专利№ 4701016披露一种包括油、胶凝剂例如氧化硅或粘土的胶态粒子、和任选的流失抑止剂的润滑脂组合物。在本发明组合物中有用的被公开的油类包括包括某些具有特定比重与性质的环烷油或石蜡油、类似性质的聚丁烯油、甘油三酯基的植物油、聚丙烯油、氯化石蜡油、和聚合的酯。胶态粒子填料优选包含氧化硅粒子诸如煅制氧化硅或沉淀氧化硅。优选的流失抑止剂包括苯乙烯-橡胶、苯乙烯-橡胶-苯乙烯、或其他的嵌段聚合物、和/或半液体橡胶诸如高粘度聚异丁烯。其他成份诸如热氧化稳定剂也可任选地存在。
美国专利№ 4701016的组合物的一个缺点，是必须包含较高量的氧化硅以符合作为润滑脂的适当的工作要求。于是，所得到的较硬稠的润滑脂是完全不适用于光纤电缆的。特别是这样的较硬稠的润滑脂在较低的温度下(即，低于约50°F)会影响光纤电缆的衰减(微弯曲)的。另外，如果氧化硅的量被降低而减少润滑的粘度的话，制剂的剪切特性将降低到低于想望的值。而且，这样的氧化硅量的减少通常会导致脱水收缩。
美国专利№ 5348669披露能提供粘度与剪切性的最佳平衡的含多羟基化合物的润滑脂组合物，以致该组合物在较低的温度下也完全适用于光纤电缆。此外，这些制剂提供的性质是能够符合这样的电缆填充用润滑脂的合适的滴淌试验、纸弯曲试验、和脱水收缩要求的。美国专利№ 5348669涉及一种用作电缆填料的润滑脂组合物，它包含约75～95重量份的、分子量至少为约3000的基本组分多羟基化合物或酯，和约2～20重量份的胶态粒子。尽管这些润滑脂组合物作为光缆填料的作用相当好，但是它们的生产成本比生产含矿物油的润滑脂的成本高得多。
此外，例如美国专利№ 4867526、5082719和5163115披露各种电缆构型，它们包括防止水通过电缆迁移的措施，这样的措施包括超高吸收性聚合物或用超高吸收性材料浸渍的带子。这些构型还使生产和/或安装的成本比含矿物油的润滑脂组合物的更高。
由于被安装的电缆较长，因此某些电缆组件是由惯用的塑料组件例如聚丙烯制成的以便降低电缆的成本并提供这样组件的多供应源。这对电缆润滑脂供应商提出一个问题，许多润滑脂组合物是与材料例如聚丙烯不相容的并能引起这些材料的降解和随之丧失各种性能。
为了补救这些问题，某些现有技术的电缆填充与注入的化合物或是用能与聚丙烯相容的更昂贵的化合物配制的，或是这样构成电缆以使不相容的化合物不与聚丙烯组件接触。优选使用成本较低并与聚丙烯相容的填充与注入化合物，以便对电缆制造商和购买者提供经济上的好处。
于是，存在一种对高性能、低成本并与聚丙烯电缆组件相容的电缆填充与注入化合物的需求。本发明提供一种解决此问题的办法。
               发明简介
本发明涉及一种用作通讯电缆、特别是光纤电缆的填充与注入材料的润滑脂组合物。此润滑脂组合物含有约25～75重量份的由蓖麻油或蓖麻醇酸酯多羟基化合物组成的油组分；约13～71重量份由(A)聚合的蓖麻油或(B)聚异氰酸酯化合物与蓖麻油或蓖麻醇酸酯多羟基化合物的反应产物作为羟基封端的的聚合物；和约4～12重量份的当混合时能赋予组合物以凝胶结构的胶态粒子。
优选的胶态粒子是憎水的煅制氧化硅、沉淀氧化硅、粘土、或它们的混合物，并且其存在量约为5～10重量份。优选的油是蓖麻油并且其存在量约为40～70重量份。优选的羟基封端的的聚合物是具有羟基值至少为70和25℃粘度至少为26沲的、聚异氰酸酯化合物与蓖麻油的反应产物并且其存在量约为20～50重量份。优选的是，油的存在量为约50～60重量份，羟基封端的的聚合物的存在量为约30～40重量份，和胶态粒子的存在量为约6～8重量份。
所说的组合物可包括高达约5重量份的流失抑止剂，0.1～2重量份的抗氧剂，高达约10重量份的阻水剂，或高达约10重量份的中空微球。所说的组合物还可包括生物杀伤剂，优选是杀菌剂，其量为高达3重量份以防止组合物变质。关于这些或其它的添加剂的详细情况将在下面作进一步的说明。
本发明还涉及包括许多光学纤维和围绕纤维的铠装和用一种上述的润滑脂组合物充填的同轴电缆。
           发明的详细说明
本发明的含多羟基化合物的润滑脂组合物适用于充填如美国专利№ 4701016、4645298、4711523、4744631和5348669中所述的光纤电缆。为了有必要了解这样的电缆的结构，在此引用这些专利作参考。多羟基化合物
用于本发明的多羟基化合物包括蓖麻油或其他的由蓖麻油、蓖麻醇酸酯二醇或其他的蓖麻醇酸酯多羟基化合物衍生的羟基封端聚合物。蓖麻油是一种天然存在的蓖麻油酸的甘油三酯。蓖麻油事实上是甘油单-、二-和三酯的混合物并具有约2.7的平均羟基官能度。其他的蓖麻醇酸酯多羟基化合物包括蓖麻醇酸酯二醇和甘醇、聚乙二醇和其他的蓖麻油酸的多羟基醇的单-、二-和多酯。美国专利№ 4812533的蓖麻醇酸酯多羟基化合物是有用的，并将该专利的内容包含于此作参考。由于其低成本和容易获得之故蓖麻油是最被优选的。
蓖麻醇酸多元醇酯可通过本技术领域公知的方法制造，例如，通过蓖麻油酸与醇类，例如乙二醇、甘油、丙二醇、己二醇、二乙二醇、二丙二醇、六亚甲基二醇、聚乙烯与聚丙烯二醇、蔗糖或山梨醇的直接酯化来制造。具体的蓖麻醇酸酯化合物包括乙二醇的单-和二-蓖麻醇酸酯，丙基单-和二-蓖麻醇酸酯，季戊四醇单-、二-、三-、四-和五-蓖麻醇酸酯，甘油蓖麻醇酸酯，1，4-环己烷二甲醇单-和二-蓖麻醇酸酯，丁二醇蓖麻醇酸酯，新戊二醇单-和二-蓖麻醇酸酯，和N，N-双(2-羟丙基)苯胺或N，N，N′，N′-四(2-羟丙基)乙二胺的单-或二蓖麻醇酸酯。羟基封端的聚合物
用于此组分的适用的聚合物包括聚合的蓖麻油或聚异氰酸酯化合物与蓖麻油或蓖麻醇酸酯二醇或多羟基化合物的反应产物。被聚合到分子量至少为约1000的蓖麻油是合用的，而从CasChem，Inc.获得的VORITE系列的聚合蓖麻油等商用化合物为优选。VORITE聚合物是通过蓖麻油与聚异氰酸酯化合物反应而生产的的一种油—聚氨酯加合物，它的羟值至少为70和分子量至少为约9000。一般说，羟值在70～130之间和分子量在2000～9000之间的被优选。
适用的异氰酸酯化合物是脂族聚异氰酸酯，环脂族聚异氰酸酯或芳族聚异氰酸酯。典型的这样的化合物是3-异氰酸根合甲基-3，5，5-三甲基-环己基-异氰酸酯(IPDI)，甲苯二异氰酸酯(TDI)，4，4-二苯基甲烷二异氰酸酯(MDI)，聚亚甲基聚苯基异氰酸酯，1，5-萘二异氰酸酯，苯二异氰酸酯，六亚甲基二异氰酸酯的缩二脲，2，2，4-三甲基六亚甲基二异氰酸酯，以及它们的混合物。其中TDI为优选。如以上所指出的那样，反应的化学计量应是能使所生成的加合物具有羟基官能度。本技术领域的熟练人员知道如何使各组分反应而得到想望的加合物。
蓖麻醇酸酯多羟基化合物还可以如基本上与蓖麻油一样的方式与聚异氰酸酯化合物反应。适用的蓖麻醇酸酯多羟基化合物包括那些在美国专利№ 4812533中所公开的蓖麻醇酸酯多羟基化合物并且它们均是有用的多羟基化合物。填料
在实施本发明中被用作填料的胶态粒子的是亲水或憎水的胶态氧化硅，优选为具有BFT表面积为约50～约40m2/gm憎水的煅制氧化硅。在实施本发明中有用的憎水的煅制氧化硅的例子是具有BFT表面积为约80～约120m2/gm、含有约5％重量碳的、可由Tuscola，Ill.，的Cabot Corporation购到的商品名为Cab-O-Sil TS 720的聚二甲基硅氧烷涂覆的煅制氧化硅。亲水的煅制氧化硅的例子是具有BFT表面积为约175～225m2/gm、标称粒径为0.012μm、比重为2.2、可由CabotCorporation购到的商品名为Cab-O-Sil M-5的煅制氧化硅。还可以使用这些材料的混合物。其他的氧化硅例如Degussa US202能被使用。
在实施本发明中有用的其他的胶态填料例如是经过或未经表面处理的沉淀氧化硅和粘土例如膨润土。部分可溶的聚合物例如聚芳酰胺和聚酰胺也可被单独或与一种或多种的其他的填料一起使用。
如果需要的话，下列的任选成份也可被包括在本发明的组合物中。
抗氧剂
如上面所指出的那样，抗氧剂可用于赋予润滑剂以增大的高温稳定性。优选的抗氧剂包括Vanderbilt Chemical V854(一种锌、硫和酚化合物抗氧剂)，Vanderbilt Chemical PLX959(一种胺和酚化合物的掺合物)，和Ciba Geigy L06或L150(它们是胺基抗氧剂)。这些添加剂的用量约为0.1～2重量份和优选为约0.5～1重量份。
Ciba Geigya Irganox 245(一种具有经验式为C34H50O8的白色结晶粉末的位阻酚化合物)也是有用的。此化合物还被称为三乙二醇双[3-(3′-叔丁基-4′-羟基-5′-甲基苯基丙酸酯)]或乙烯双(氧乙烯基)双(3-叔丁基-4-羟基-5-甲基氢化肉桂酸酯)。与聚醚键相连的其他的双位阻酚环应能提供可比拟的结果，但是Irganox 245由于其在化学上的更易工业取得性而被优选。
为了测定特定的抗氧剂是否适用于本发明，可以进行Belcore氧抑止试验(“OIT”)。将润滑脂试样置于氮气压力下和190℃的量热器的舟皿中。此后，泵入纯氧到量热器中并测定润滑脂的变化。为了提供适用的润滑脂，剩余的材料必须是能具有至少为约20分钟并且优选为30分钟的在190℃与纯氧环境中的氧化诱导时间。在本发明的润滑脂制剂中使用0.75％重量的V854或PLX959能使润滑脂在此试验中具有接近50分钟或更高的氧化诱导时间。这些例子说明某些润滑脂制剂的优选的OIT值。
流失抑止剂
有效的流失抑止剂包括聚氨酯弹体、聚酯弹体、丁二烯-丙烯腈、聚丙烯酸酯或丙烯酸酯的共聚物、橡胶嵌段共聚物，并且其存在量为高达5重量份和优选为约1～4重量份。这些材料是本技术领域的熟练人员所熟知的并且它们可以被单独或以各种混合物的形式使用。微球
微球可以以高达约10重量份和优选为1～5重量份的用量被添加到本发明的润滑脂制剂中。一般说，适用的微球是由各种材料诸如热塑性树脂、热固性树脂、陶瓷、玻璃和烧结的金属中的任一种材料形成的。微球的直径范围约在1～200微米之间并且优选在50～130微米之间。它们通过混合被较均匀地分散于整个的润滑脂中并能降低整个组合物的成本。用于本发明的几种合用类型的热塑性塑料微球是例如由EXPANCEL和Pierce & Stevence销售的热塑性塑料微球。这样的微球另外包含在其上的涂层。由Pierce & Stevence以DUALITE销售的热塑性塑料微球包含在其上的任何一种的涂层，例如滑石、碳酸钙、氧化锌、二氧化钛、云母、硫酸钙、硫酸钡、氧化锑、粘土、氧化硅、和三水合铝。在此作为参考文献的Morehouse的美国专利№ 3615972披露许多被用来制造此类也适用于本发明的微球的方法。超吸收剂
还可包含组合物重量的高达约10重量份并且优选为约1～5重量份的超吸收剂。超吸收剂是亲水性材料，在不溶于被吸收的流体的情况下它能在压力下吸收和保留水。参见美国专利№ 4867526和其中所披露的材料，在此特意将此文献编入作参考。各种特性诸如酶稳定性、生物可降解性、吸收能力和吸收率被用来表征超吸收性材料。
当今可得到的两种主要的超吸收剂是纤维素或淀粉接枝的共聚物和合成的超吸收剂。主要有二大类的合成的超吸收剂。它们是聚电介质和非电介质。聚电介质是最重要的并被分成四类：聚丙烯酸超吸收剂，聚丙烯腈基超吸收剂，聚马来酐乙烯基单体超吸收剂和聚乙烯醇超吸收剂。其中，聚丙烯酸和聚丙烯腈基超吸收剂是最常用的。正如与纤维素接枝共聚物超吸收剂一样，合成的超吸收剂的能力是随着盐浓度的增加而减少的，但是近来已配制出在盐存在时使用的产品。这种耐盐的超吸收剂的公开材料可从美国专利№ 5163115中发现，该专利还特意被编入于此作参考。
聚丙烯酸类超吸收剂包括丙烯酸和丙烯酸酯的均聚物与共聚物。单体单元通常被聚合而产生水溶性聚合物，然后通过离子和/共价键交联赋予聚合物以不溶性。聚合物的交联可以用多价阳离子，辐照，或用交联剂来实现。产物的吸收性是由可电离的基，通常是羧酸酯，和交联密度决定。
交联密度不仅影响吸收性而且还影响吸收所需的时间与所形成的凝胶的强度。一般说来，交联密度越高所形成的凝胶的强度就越强。达到吸收能力的时间是随着交联密度的增加和吸收能力的减少而减少的。
本发明的组合物还可包含其量为0.01～3重量份的其他的添加剂诸如生物杀伤剂和杀菌剂。优选的杀菌剂是由Calgon Corporation制造的TK 100，其常用量为0.05～0.25重量份。在光纤电缆中放置这些组合物
将上述成份混合，本发明的润滑脂的特征是具有高穿透性的非滴淌性和低的屈服应力。就润滑脂而言高穿透能力使其具有更好的流动性，即，具有更低的使用粘度以致电缆能被更容易地被润滑脂所充填。此外，本发明提供超过现有技术制剂的优点。上述的优越的加工性的不寻常处在于在易于充填的热与剪力下材料能够尽可能的薄。此点已被本发明的填充组合物的低于约10～30的屈服应力和本发明的注入组合物的约50～150的屈服应力所证实。于是。本发明的润滑脂能更容易和更快充填电缆，并由此避免了能在光纤电缆中引起衰减的微弯曲的困难。
当将润滑脂作为填充化合物引入到光纤电缆中时，重要的是使粘度达到尽可能低以致使纤维不会被移动。这点是通过在高剪力下将润滑脂引入到电缆中来实现的。润滑脂组合物被保留在贮槽或鼓式泵(drumpump)的鼓中，一种活塞式鼓式泵与此相连。此泵引起低的剪力并使润滑脂从鼓中流出，而进入到被跟踪和加热的而使在其中的润滑脂保持在至少约为80℃温度的输送导管或管子中。然后润滑脂通过在例如从约5000到高达约20000转/秒的高剪力条件下操作的齿轮泵。泵的出口管将将润滑脂送入到处于光纤电缆周围的管心，以使润滑脂进入到纤维周围的电缆中的方式挤出。润滑脂在温度约500～600°F、优选为约550°F下被挤入到电缆中。与现有技术的润滑脂不同，本发明的制剂在该温度时是稍稳定的。
当所说的组合物被用作注入化合物时，可使用类似的程序，除了较少考虑引起纤维的移动外，因为它们置于铠装与填充化合物之中。如本技术领域的熟练人员所知，注入化合物被用于电缆的铠装与外套之间的开口部位。有利之处在于本发明的组合物由于不会使电缆的任何聚丙烯组分变质，因而既可被用作填充料又可被用作注入物。
本发明的组合物能通过为获得适用作为光纤电缆的填充料或注入料的润滑脂的各种适当的试验。这些试验包括在25℃下使用0.1毫米的渗透剂做的纸流失试验。此试验被述于下：
步骤
准备下列材料：5ml注射器；直径11cm的1型滤纸；Pyrex表面玻璃(直径12cm)；600ml Pyrex烧杯；试验室用刮刀；分析天平；镊子；剪子；和被设定在80℃的强制通风烘箱。
1.用试验室用刮刀将润滑脂化合物装入到注射器中。慢慢地按压活塞以便排除空气泡。
2.切出一块1英寸×1英寸方块的滤纸；称重(WT1)并记录(准确到0.0001克)。
3.从注射器中将1ml的化合物缓慢地加到滤纸块上而形成圆斑(在斑边周围留有某些空白使圆斑能扩展)。称出此“试样块”的重量并将此值作为WT2记录之。
4.称出直径为11cm的圆滤纸的重量(WT3)，并将其放置于表玻璃上。
将“试样块”放置在滤纸的中央，并用600ml烧杯覆盖。
5.让试样块在室温下静置16小时。
6.称出试样块重量(WT2A)和大圆滤纸的重量(WT3A)。
7.将试样块重新放到烧杯下，并将整套组合件放置到烘箱中。静置24小时。
8.从烘箱中取出并在大理石表面上冷却5分钟。称出试样的重量(WT2B)和圆沪纸的重量(WT3B)。注意任何的颜色变化。
9.扔掉试样块与滤纸。
10.当处理试样块与圆滤纸时，仅使用镊子。小心从试样块掉失水份与所有的外部粒子。
计算的结果如下：
计算
“A”值被用来计算在室温下放置16小时后的重量变化。“B”值被用来测定在80℃下再放置24小时后的重量变化。
1.初始重量＝(WT2)-(WT1)
2.重量损失＝(WT2)-(WT2A或WT2B)
3.％重量损失＝重量损失×100/初始重量
4.滤纸重量的增值＝(WT3A或WT3B)-(WT3)
5.挥发重量
a.如果(重量损失)-(滤纸重量的值)＞0
b.如果(重量损失)-(滤纸重量的值)≤0
6.％挥发物重量＝挥发物重量×100/初始重量
7.％非挥发性物质分离＝％重量损失-％；挥发物重量
量测误差
由于反复的处理试样之故，出现某些误差是意料中的，特别是在室温下计算挥发物重量损失时。所有的重量应被记录到最接近0.0001克。全部的计算结果应尽可能全都报导。被评估的化合物应至少同时测定三个试样。然后将所得的％值平均以测定出％重量损失和％非挥发物分离。
少于约15的值被认为是良好的而少于约10的值被认为是优越的。
另一种性能测定是锥体流失试验(cone bleed test)。该试验是如下进行的：设备
1.锥体—带有金属丝提手的60网目的镍筛网锥体。此筛网锥体具有3600个孔/平方英寸、0.0075英寸金属丝、0.011英寸的孔。它由Newark Wire Cloth制造。
2.烧杯-250ml玻璃烧杯。
3.棒—由玻璃或其他材料制成，它被用来支持烧杯中的筛网锥。
4.烘箱—空气烘箱，带有可调节的温度控制器(±1℃)。
5.干燥器。
6.天平—读数到0.1mg。
7.刮刀—金属制，平的。步骤
1.预热烘箱到80℃。
2.在分析天平中称量干净的烧杯。记录重量接近到mg(重量W1)。
3.称量空锥体。记录重量接近到mg(重量W2)。
4.使用刮刀将试样放置在锥体中使润滑脂的顶面是平突的(以防止在试样顶面上截留油)并称重。记录重量接近到mg(重量W3)。
5.将锥体悬置于烧杯中的玻璃棒上。不让锥体与杯壁接触。
6.称量整套组合件到接近mg(重量W4)。
7.将烧杯与锥体放置于设定在80℃的烘箱中。
8.经30小时从烘箱中取出锥流失装置并将其放置于干燥器中以冷却到室温(约一小时)。
9.当冷却时，称量整套组合件(重量W5)。
10.朝烧杯内侧轻敲锥体以除去任何粘附到顶面的油。
11.称量烧杯。记录重量到接近到mg(重量W6)。
12.计算锥体流失和蒸发。计算
1.为了计算百分锥体流失使用下面的方程式：式中：W6＝在经过合适的炉温时间后的烧杯的重量W1＝原始的烧杯重量W3＝原始的锥体与试样的重量W2＝锥体的重量
2.为了计算百分蒸发而使用下面的方程式：
Figure A9619677800132
式中：
W4＝锥体、试样、棒、和烧杯的原始重量
W5＝在烘箱中经合适的时间后的锥体、试样、棒、和烧杯的重量
W3＝锥体和试样的原始重量
W2＝锥体的重量
少于约3的值被认为是具有代表性的良好的润滑脂制剂。
                    实施例
现结合下列的实施例对本发明的范围作进一步的介绍，提供这些实施例的目的仅为了说明本发明的优选的实施方案，而不是对本发明的范围加以任何的限制。除了另有说明者外，在这些实施例中所有的份数均以重量表示。
实施例1～29：
通过如上所述的在高剪力下将各成份混合在一起而制备表1中所示的各制剂。对这些制剂的测定结果被示于表2中。尽管未测定实施例1～3中的制剂的性质，但是它们显然能生产出良好的润滑脂制剂。每种润滑的所有性质并未全部被测定，因为为了研究特定性质诸如屈服应力、纸渗透等的变化仅对在先的制剂进行改进，以研究由于这些改进所引起的变化。
                      表1-制剂
                       实施例组分      对照物      对照物      1       2      3       4      5      6      7     8      9      10
          A           B蓖麻油      90                   65.65   66.15  66.65   68     58     58      58    58.05  58.05  58.05VORITE 105               93.05VORITE 125                         25      25     25      25     35     35      35    35     35     35US 202      7TS 720                  6        7.5     7      6.5     6      6      4       5     6      6      6PLX 959                                                                              0.75   0.75   0.75TK 100                  0.2      0.05    0.05   0.05                          0.2   0.2    0.2    0.2L 150                           1.8     1.8    1.8V 854      3           0.75                            0.75   0.75   0.75    0.75V 974                                                                2       1
                          表1-制剂(续)
                              实施例组分     11   12      13    14  15     16     17     18     19     20    21     22蓖麻油    59   36.05   43    43  51.96  53.83  53.21  54.65  54.95  61.2  59.1   53.35VORITE 110               50VORITE 115                     50VORITE 125  35   54.5              31.24  32.77   31.99  36.25  36.25  30   28.98  26.16TS 720    5    8.5     6     6   6       7      8      8.5    8      8    6      4PX 959         0.9               0.75                                     0.75   0.8TK 100         0.05              0.05    0.05   0.05   0.05  0.05   0.2   0.05   0.05V 854     0.75         0.75  0.75        0.75   0.75   0.75  0.75   0.75DUALITE6032  AE                           5       5      5                         5.11   5.22SAB 800 HS                         5       1      1                                10
                       表1-制剂(续)
                         实施例组分       23      24      25      26       27       28       29蓖麻油      58.2    55.48   57.48   57.75    58.45    57.45    58.45VORITE 110VORITE 115VORITE 125    35      27.72   28.72   28.45    28.75    28.75    28.75TS 720      6       6       6       6        5        5        6PX 959      0.75    0.75    0.75    0.75     0.75     0.75     0.75TK 100      0.05    0.05    0.05    0.05     0.05     0.05     0.05DUALITE               5       5       7        7        6        56032AESAB 800 HS            5       2                         1        1
表1的注解：
蓖麻油是CasChem，Inc.的AA标准级蓖麻油。
VORITE 105是一种具有羟值为130和25℃粘度为26沲的蓖麻油加合物。
VORITE 110是一种具有羟值为102和25℃粘度为115沲的蓖麻油加合物。
VORITE 115是一种具有羟值为93和25℃粘度为192沲的蓖麻油加合物。
VORITE 125是一种具有羟值为72和25℃粘度为900沲的蓖麻油加合物。
US 202是一种得自Degussa的胶态氧化硅。
TS 720是一种得自Cabot Corporation的胶态氧化硅。
PLX949是得自Vanderbilt Chemicals的一种胺与酚化合物的掺合物的抗氧剂。
TK 100一种得自Calgon Corpration的杀菌剂。
L 150是一种得自Ciba Geigy的胺基抗氧剂。
V 854是一种得自Vanderbilt Chemicals的锌、硫和酚化合物的抗氧剂。
V 974是一种得自Vanderbilt Chemicals的金属和酚化合物的抗氧剂。
DUALITE 6032AE是得自Pierce & Stevens的玻璃微球。
SAB 800HS是一种得自Stockhausen，Inc.的超吸收剂。
                表2-结果
                 性  质实施例    粘度    纸渗透      锥体流失             其他
      (cps)对照物A    9.4     27.9         4.75对照物B    15.7    19.7         2.44        19.6    12.2         1.85        23.2    9.4          1.35       OIT＝55分屈服应力＝25Pa6        24.1    11.8         0.37        24.2    10.5         0.84          屈服应力＝17Pa8        22.9    13.7         1.8           屈服应力＝43Pa9        25.9    15.6         1.210       28.6    10.3         1.4        OIT＝67分屈服应力＝28Pa11       19.1    10.2         1.7412       49.1                 0.7213       15.5    17.5         2.214       14.4    17.1         1.815                                           屈服应力＝39Pa16                                           屈服应力＝36Pa17                                           屈服应力＝51Pa18                            0.47           屈服应力＝71Pa19                            0.43           屈服应力＝52Pa20                            0.63       OIT＝55分屈服应力＝52Pa21               13.6         1.63           屈服应力＝34Pa22               16.4         1.87           屈服应力＝11Pa23               11.1         0.924                            0.5            屈服应力＝42Pa25                            0.7            屈服应力＝28Pa26                            0.8            屈服应力＝25Pa27                            2.5            屈服应力＝15Pa28                            1.329                            1.1            屈服应力＝27Pa
就这些实施例而言，实施例5和10具有非常好的OIT值，实施例7、22和27具有非常低的屈服应力值。实施例12具有非常高的粘度，它对某些应用中是有利的。实施例6、7、18、19、20、23、24、25、和28具有最好的锥体流失性，而实施例4-8、10、11、21和23具有最好的纸渗透性。在这方面，实施例23提供最好的抗弯曲性。
这些结果显示，能够根据想望的要求来调整粘度、流失率和屈服应力值。例如，对填充化合物而言，低屈服应力组合物被优选。粘度约为12～30000的特别适用作填充化合物，而更高粘度的组合物可用作注入化合物。根据具体电缆形状或结构的其他要求可以要求不同的性质，这些可以根据上述各组分的混合物来选择。实施例30
聚丙烯填充化合物的吸收性试验是使用各种电缆的润滑脂进行的，并且其结果被示于下表3中。将聚丙烯和润滑脂试样接触和保持在80℃一段记录的时间，并测定被聚丙烯吸收的润滑脂的百分率。
                表3吸收率(％)
润滑脂组合物或类型      1周后     2周后    3周后矿物油—聚丁烯       12.72    13.49    14.06聚α-烯烃—聚丁烯(制造商A)   7.58     8.64     9.19聚α-烯烃—聚丁烯(制造商B)   4.12     5.48     6.14
   本发明的实施例23     0.14     0.25     0.30
上述的资料显示本发明的润滑润滑脂，与常规的制剂相比，是与聚丙烯高度相容的。
尽管此处所披露的本发明被完全认为是能实现上述目的的，但是考虑到本领域的熟练的技术人员能作出许多的改进和另外的实施方案，因此只要它们处于本发明的精神与范围内，所附的权利要求书应包括所有这样的改进与实施方案。

Claims (15)

1.一种用作电缆填充料的润滑脂组合物，包含约25～75重量份的含蓖麻油或蓖麻醇酸酯多羟基化合物的油组分；约13～71重量份由(A)聚合的蓖麻油或(B)聚异氰酸酯化合物与蓖麻油或蓖麻醇酸酯多羟基化合物的反应产物构成的羟基封端聚合物；和约4～12重量份的当混合时能赋予组合物以凝胶结构的胶态粒子。
2.权利要求1的组合物，其中所说的胶态粒子是憎水的煅制氧化硅、沉淀氧化硅、粘土、或它们的混合物。
3.权利要求1的组合物，其中所说的胶态粒子的存在量约为5～10重量份。
4.权利要求1的组合物，其中所说的油的存在量约为40～70重量份和所说的羟基封端的的聚合物的存在量约为20～50重量份。
5.权利要求1的组合物，其中所说的油是蓖麻油。
6.权利要求1的组合物，其中所说的羟基封端的的聚合物是具有羟值至少为70、25℃时粘度至少为26沲的、聚异氰酸酯化合物与蓖麻油的反应产物。
7.权利要求6的组合物，其中所说的油是蓖麻油和其存在量约为50～60重量份，所说的羟基封端的的聚合物是聚异氰酸酯化合物与蓖麻油的反应产物，其存在量为约30～40重量份，所说的胶态粒子是氧化硅、粘土、或它们的混合物其存在量为约6～8重量份。
8.权利要求1的组合物，还包含其量为高达约5重量份流失抑止剂。
9.权利要求8的组合物，其中所说的流失抑止剂的存在量为约1～4重量份并包括聚氨酯弹体、聚酯弹体、丁二烯-丙烯腈、聚丙烯酸酯、丙烯酸酯的共聚物、氯化橡胶、或热塑性嵌段共聚物。
10.权利要求1的组合物，还包含其量为约0.1～2重量份的抗氧剂。
11.权利要求1的组合物，还包含其量为高达约10重量份的阻水剂。
12.权利要求11的组合物，其中所说的阻水剂是超吸收聚合物并且其量为约1～5重量份。
13.权利要求1的组合物，还包含其量为高达约10重量份的中空微球。
14.权利要求13的组合物，其中所说的微球是由玻璃、陶瓷、塑料或它们的混合物制成的并且其存在量为约1～5重量份。
15.一种包含许多光学纤维和围绕所说的纤维的铠装并用权利要求1的组合物充填的同轴电缆。
CN96196778A 1995-07-12 1996-06-24 光纤电缆用的聚丙烯相容的润滑脂组合物 Pending CN1195359A (zh)

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