CN1149882A - 导电聚合物组合物 - Google Patents
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Abstract
一种包含分散在聚合物成分中的粒状导电填料的导电聚合物组合物。该聚合物成分含有第一聚合物,该第一聚合物,(i)含量为该聚合物成分总重量的25-75%,(ii)它是聚乙烯;以及第二聚合物,该第二聚合物,(i)其含量为该聚合物成分总重量的25-75%,(ii)它包含由第一单体,即乙烯,和第二单体,即通式为CH2=CHCOOCmH2m+1,其中m至少是4的丙烯酸烷基酯,衍生而来的单元。获得的组合物能用于制造电器件(1),例如电路保护器件,这种器件与含有传统的导电聚合物组合物的器件相比,电阻率低、PTC反常升高值大而且热和电稳定性好。
Description
发明领域
本发明涉及导电聚合物组合物以及含有这种组合物的器件和组装件。
发明背景
导电聚合物组合物和含有这类组合物的电器件是众所周知的。这类组合物包含一种聚合物成分以及分散在该成分中的粒状导电填料,例如碳黑或金属。导电聚合物组合物公开在美国专利号4,237,441(范·柯尼恩伯格(Van Konynenburg)等)、4,388,607(托伊(Toy)等)、4,534,889(范·柯尼恩伯格(Van Konynenburg)等)、4,545,926(佛茨(Fouts)等)、4,560,498(霍尔斯马(Horsma)等)、4,591,700(索波利(Sopory))、4,724,417(奥(Au)等)、4,774,024(迪普(Deep)等)、4,935,156(范·柯尼恩伯格(Van Konynenburg)等)、5,049,850(埃文斯(Evans)等)、5,250,228(贝格里(Baigrie)等),以及正在审查中的美国专利申请号07/894,119(钱德勒(Chandler)等,1992年6月5日提交)、08/085,859(楚(Chu)等,1993年6月29日提交)和08/173,444(钱德勒(Chandler)等,1993年12月23日提交)。上述专利和申请中每项的公开内容均作为参考收入本文。
这类组合物常表现出正温度系数(PTC)行为,即它们的电阻率,通常在较窄的温度范围内,随温度的升高而增加。出现这种升高时的温度即是转变温度Ts,该温度可以这样来确定:即在PTC元件电阻的常用对数(log)值对温度的曲线上,分别位于斜率显示出急剧改变的那部分曲线的两侧之一的、基本上为直线的两部分的延长线交点所对应的温度。从25℃时的电阻率(ρ25)至峰值电阻率(ρ峰,即组合物在Ts以上所表现出的最大电阻率)的增加值是PTC反常升高。
PTC导电聚合物组合物尤其适合用于这样一类电器件,例如对环境温度、电流、和/或电压条件变化作出反应的电路保护器件、加热器以及传感器。对于许多用途来说,希望组合物的电阻率尽可能低,PTC反常升高尽可能高。电阻率低,则器件可以做得小,其电阻也低。这样的器件在印刷电路板或者其他衬底上只需很小的空间,在正常操作时对电路的电阻贡献很小。PTC反常升高大,则使器件能经受住必要的外加电压。虽然导电聚合物组合物的电阻率可以借助加入更多的导电填料来降低,然而通常的情况是,这样一来PTC反常升高值就降低了,这可能是由于对PTC反常升高有贡献的结晶聚合物的含量降低了的缘故,或者是由于通过物理方法增强了聚合物成分,从而降低了在熔点温度下的膨胀所致。
除低电阻率和高PTC反常之外,导电聚合物组合物的转变温度的高低也是重要的。某些用途,例如用于机动车的场合,其中电器件被装在罩子之下,要求Ts足够高,以便使该聚合物成分不致因高环境温度而受到不利的影响。另一些用途,例如用来保护电池,则要求Ts足够低,以便使该器件转变为高温/高电阻状态时其衬底或周围的零部件不致因受热而损坏。
发明简述
为了达到上述目的,采用了由两种或更多种聚合物的共混物来制备组合物,其中每种在挑选时都要求对最终混合物的性能作出贡献。例如,在由高密度聚乙烯(HDPE)和乙烯/丙烯酸共聚物(EAA)组成的混合物中,熔点较低的共聚物触发Ts,而结晶度较高的聚乙烯则对提高PTC反常升高值作出贡献。
我们现已发现,用含有至少4个碳原子的烷基的丙烯酸烷基酯代替至少一部分EAA,可以使性能得到改善。所得到的组合物与传统的组合物相比,低电阻率特性改善了,PTC反常升高值提高了,同时电气和热稳定性也有所改善。另外,消除存在于EAA中的丙烯酸官能团能降低组合物的酸性,从而减少当组合物应用于电器件时对于昂贵的耐酸镍金属箔电极的需要。就第一方面而言,本发明公开一种导电聚合物组合物,包含:
(A)一种聚合物成分,其中含有
(1)第一聚合物,(a)其含量为该聚合物成分总重量的25-75%,(b)它是聚乙烯,和
(2)第二聚合物,(a)其含量为该聚合物成分总重量的25-75%,(b)它包含由(i)第一单体,即乙烯和(ii)第二单体,即通式为CH2=CHCOOCmH2m+1,其中m至少是4,的丙烯酸烷基酯,衍生而来的单元;以及
(B)一种分散在该聚合物成分中的粒状导电填料。
就第二方面而言,本发明提供一种电器件,包括
(A)由本发明第一方面的导电聚合物组合物构成的一种元件;和
(B)至少一个适合用来将该导电聚合物元件连接到电源上的电极。
就第三方面而言,本发明提供一种组装件,包括
(A)一种电路保护器件,包括一种由本发明第一方面的导电聚合物组合物构成的元件和至少一个适合用来将该导电聚合物元件连接到电源上的电极,和
(B)与上述电路保护器件电气相连的电池。
附图简述
图1是本发明器件的平面视图;
图2是一种采用本发明的组合物制作的器件和一种传统器件的电阻随温度变化的曲线;
图3是本发明器件的表面温度随外加电压变化的曲线;
图4是器件在不断提高的外加电压作用下的完好率曲线;以及
图5是熔融热随组合物中乙烯共聚物重量百分数而变化的曲线。
发明详述
这种组合物的聚合物成分包含第一和第二聚合物,每一种都是结晶的,就是说其结晶度至少是10%,优选地至少20%。该聚合物成分通常构成组合物总重量的30-80%(重量),优选地构成35-75%(重量),尤其优选40-70%(重量)。
该第一聚合物是聚乙烯,例如高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、线型低密度聚乙烯,或者上述聚乙烯中两种或更多种的混合物。对于要求暴露在高于约100℃的热环境下仍保持完好的组合物,该聚乙烯优选地为高密度聚乙烯,即密度为至少0.94g/cm3,一般为0.95-0.97g/cm3的聚乙烯。该第一聚合物构成该聚合物成分总重量的25-75%,优选30-70%,尤其优选35-65%。
该第二聚合物是乙烯共聚物或三元共聚物,其中第一单体是化学式为-CH2CH2-的乙烯,第二单体是通式为CH2=CHCOOCmH2m+1,其中m至少为4而最大为8,例如等于4的丙烯酸烷基酯。该第二单体构成该第二聚合物重量的至多25%,优选地至多20%,尤其优选至多15%,例如5-10%.。优选的共聚物是乙烯/丙烯酸丁酯(也叫做乙烯/丙烯酸正丁酯)共聚物和乙烯/丙烯酸异丁酯共聚物,其中m=4。
当第二单体是三元共聚物时,它包含第三单体,其含量为该第二聚合物重量的至多10%,优选地至多8%,尤其优选至多5%。合适的第三单体是甲基丙烯酸缩水甘油酯和马来酐。
该第二聚合物构成聚合物成分总重量的25-75%,优选30-70%,尤其优选35-65%。
对于某些用途而言,可能希望把第一和第二聚合物与一种或多种附加的聚合物,例如弹性体、非晶态热塑性聚合物或其他种结晶聚合物掺混,以便获得特定的物理或热性能,例如柔性或尽量高的耐热性。
为了充分发挥第一和第二聚合物的混合物的优势,优选的是,这两种聚合物能共结晶,即两种结晶聚合物中每一种的至少一部分与另一种聚合物互为同系物。当第一和第二聚合物以熔融状态紧密混合时,第一聚合物的同系部分与第二聚合物的同系部分形成晶体,即共结晶。据认为,本发明组合物在电和热稳定性方面的改善是由于这种共结晶作用所致。共结晶导致在熔融热方面的改善和PTC反常升高的提高。非导电聚合物,即不包含任何导电填料的聚合物成分,的共结晶度可采用线性混合规则,例如可以采用这种规则并结合下面描述的步序来确定。有关混合规则,可参见“混合物性质的预测:科学和工程中的混合规则”,劳伦斯E.尼尔森著(MarcelDekker公司出版,1978)一书的5-9页,该部分内容作为参考收入本文。按照这一规则,混合物熔融热的预测值的计算按下式进行:
PB=PHDPE(wt%HDPE)+PCO(wt%乙烯共聚物)其中P代表给定的性质(即熔融热),PB是混合物熔融热的预测值,PHDPE是第一聚合物(即100%HDPE)熔融热的测定值,PCO是第二聚合物(即100%乙烯共聚物)熔融热的测定值。混合物的预测值PB与混合物熔融热的实际测定值之间的差是共结晶程度的一个度量。
分散在聚合物成分中的粒状导电填料可以是任何合适的材料,包括碳黑、石墨、金属、金属氧化物、导电涂层玻璃或陶瓷珠、粒状导电聚合物或上述的某种组合。填料的形状可以是粉末、珠状、片状、纤维或任何其他合适的形状。导电填料的需要量是根据要求的组合物电阻率和导电填料本身的电阻率来确定的。对于许多组合物而言,导电填料构成该组合物总重量的20-70%(重量),优选25-65%(重量),尤其优选30-60%(重量)。
该导电聚合物组合物可以含有附加的成分,例如抗氧剂、惰性填料、非导电填料、辐射交联剂(常常被称之为辐射促进剂或交联增强剂)、稳定剂、分散剂、偶合剂、除酸剂(例如碳酸钠)或其他成分。这些成分一般的含量至多为聚合物总重量的20%。
导电填料和其他成分的分散可以通过熔体加工、溶剂混合或任何其他合适的混合手段实现。混合之后,可以采用任何合适的方法将组合物熔融成形,从而生产出用于电器件中的导电聚合物元件。合适的方法包括熔体挤塑、注塑、压塑和烧结。对许多用途而言,希望将组合物挤塑成片材,然后再从片材上裁切、削片或采用其他方法取出元件。元件可以是任何形状的,例如矩形、方形、圆形或环形。根据设计的最终用途之不同,可以对组合物实施各种不同的技术处理,例如成形后进行交联或热处理。交联可以通过化学手段,也可以通过辐射,例如采用电子束或钴60伽马辐射源,来达到,而且这一步既可以在安装电极之前,也可以在安装电极之后进行。本发明器件使用的交联剂量为总共200兆拉德当量,不过对于低压用途(例如低于60伏),宜采用低得多的水平,例如5-20兆拉德。
该组合物一般表现出正温度系数(PTC)行为,即在较窄的温度范围内其电阻率显示出急剧的升高,虽然某些用途的组合物也可能表现出零温度系数(ZTC)行为。在本文中,“PTC”一词指的是一种组合物或器件,其R14的数值至少是2.5和/或R100值至少是10,而优选的是,这种组合物应具有至少6的R30数值,其中R14是14℃宽的区间的终点与起点间电阻率的比值,R100是100℃宽的区间的终点与起点间电阻率的比值,R30是30℃宽的区间的终点与起点间电阻率的比值。一般而言,具有PTC行为的本发明组合物所显示出的电阻率升高幅度要比上面指出的下限数值大得多。
本发明的组合物可用来制备电器件,例如电路保护器件、加热器、传感器或电阻器,其中由该导电聚合物组合物构成的元件与至少一个适合用来将该元件连接到电源上的电极处于物理和电气的接触。电极的类型取决于元件的形状,可以是,例如实心或多股绞合线、金属箔、金属网或金属油墨层。本发明的器件可以是任何形状的,例如平面的、轴对称的、或“8”字型的,但是尤其有用的器件包括两只薄片电极,优选金属箔电极,以及夹在二者之间的导电聚合物元件。特别适合的薄片电极公开在美国专利号4,689,475(Matthiesen),4,800,253(Kleiner等),以及正在审查之中的美国专利申请号08/255,584(Chandler等,1995年6月8日提交),上述中每一个的公开内容均作为参考收入本文。在薄片电极上可以连接附加的金属引线,例如金属丝或条子形式的,以便使之与电路电气地相连。另外,还可以使用用以控制器件热输出的元件,例如一个或多个导热端子。这些端子可以是金属板形式的,例如钢、铜或黄铜的,也可以是翅片状的,它们或者直接与电极相连,或者通过中间层,例如焊药或导热粘合剂与之相连。例如可参见美国专利号5,089,801(Chan等),以及正在审查的美国专利申请号07/837,527(Chan等,1992年2月18日提交)。对于某些用途而言,优选将器件直接装到电路板上。这类安装技术的实例公开在美国专利申请序列号07/910,950(Graves等,1992年7月9日提交)、08/121,717(Siden等,1993年9月15日提交)以及08/242,916(Zhang等,1994年5月13日提交),以及国际专利申请号PCT/US93/06480(Raychem公司,1993年7月8日提交)。上述专利及申请中每一项的公开内容均作为参考收入本文。
本发明的组合物可以做成器件组合件,其中该组合物与二块金属薄片电极接触,而一般是夹在这二者之间。所谓“器件组合件”涵盖可直接与其他电气零部件连接的器件,也包括某种构造,它在经过必要的进一步加工之后,可以再被分成许多个电器件。这类器件组合件公开在美国专利申请号08/121,717(Siden等,1993年9月15日提交)和08/242,916(Zhang等,1994年5月13日提交),上述的公开内容作为参考收入本文。
电路保护器件的电阻一般在100欧姆以下,优选50欧姆以下,尤其优选30欧姆以下,特别优选20欧姆以下,最优选10欧姆以下。就许多用途而言,电路保护器件的电阻小于1欧姆,例如0.010-0.500欧姆。当用于电路保护器件时,导电聚合物组合物在20℃时的电阻率,r20,小于10欧姆-厘米,优选小于7欧姆-厘米,尤其优选小于5欧姆-厘米,特别优选小于3欧姆-厘米,例如0.005-2欧姆-厘米。加热器的电阻一般为至少100欧姆,优选至少250欧姆,尤其优选至少500欧姆。当该电器件是加热器时,其导电聚合物组合物的电阻率优选地高于用于电路保护器件的电阻率,例如为102-105欧姆-厘米,优选102-104欧姆-厘米。
本发明的组合物尤其适合制作用于电池用途的电路保护器件。特别是该电路保护器件被电气地连接到一个组装件里的一个或多个电池上的情况。电池,尤其是那些,例如用在可充电电池组内的镍/镉电池和镍/金属氢化物电池,必须加以保护,使之免受因充电器有毛病或过度充电而造成的外部短路或过度充电的损坏。另外,镍/金属氢化物电池当温度超过约80℃时就会冒气,从而释放出气体,例如氢气和H2O2。为了保护这种镍/金属氢化物电池,电路保护器件必须“阻断”,即在受到80℃的环境温度以及某一规定的电流,阻断电流IT,的作用时从它的低电阻、低温状态转变为它的高电阻、高温状态。IT与器件的几何形状及电阻,以及热环境等因素有关,而通常小于约2安培,例如为约1安培。但是,要在正常使用的状态下正常工作,当在60℃下受到接近额定电流的作用时,该器件不得阻断,就是说,它还必须有一个规定的保持电流IH。比如说,要能正常工作,要求一种器件应有至少1安培的60℃保持电流IH,同时其80℃的阻断电流IT最高为1安培。有用的本发明器件,其80℃的IT与60℃的IH之比最大是1.3,优选最大1.25,尤其优选最大1.20,而且其80℃的IH与60℃的IH之比最大为0.60,优选最大0.55,尤其优选最大0.50。本发明的组合物,特别是含有作为第二聚合物的乙烯/丙烯酸丁酯的组合物,能生产出满足上述条件的器件,然而以乙烯/丙烯酸共聚物为主要成分的传统组合物所制成的器件则不能。
下面将结合附图来说明本发明,其中图1是表示本发明的器件1的平面视图。导电聚合物元件3被夹在两个金属薄片电极5、7之间。
现在通过下列实例来说明本发明,其中实例1和2为对比例。
实例1-10
对于每一个实例,将表1中规定的配料置于布拉本德(Brabender)混炼机中,在加热至175℃下以60转/分的转速混炼15分钟。将混合物挤塑成0.25毫米(0.010英寸)厚的片料。把从片料上裁下来的小片夹在两块2.5毫米(0.001英寸)厚的、镀镍的电沉积薄铜片(由Fukuda公司提供)之间,然后层合,或采用压塑,或采用夹辊压合。采用1.5兆电子伏特的电子束对层合物施以10兆拉德的照射,然后裁成器件。对于实例1-3,用于湿度试验的器件的尺寸为12.7×12.7毫米(0.5×0.5英寸)。所有其余的器件均为环状园片,外径为13.6毫米(0.537英寸),内径为4.4毫米(0.172英寸)。进行了如下的试验。对大多数试验而言,测定了器件在25℃时的初始电阻,Ri。在试验过程中隔一定时间将器件从夹具上取下。在25℃下放置1小时后,测定最终电阻Rf并算出比值Rf/Ri。
湿度试验
将器件放入保持在85℃和85%湿度的烘箱内并定期地取出。Rf/Ri的数值显示,含有乙烯/丙烯酸丁酯共聚物的器件的电阻增加幅度比含有传统的乙烯/丙烯酸共聚物的器件要小。
耐阻断疲劳
对由器件与开关、15伏特的直流电源、将初始电流限制在40安培的固定电阻器串联而成的电路中的器件进行了试验。定期地使器件突变至高电阻状态,然后取下。试验结果表明,含有乙烯/丙烯酸丁酯(EBA)组合物的器件比含有乙烯/丙烯酸(EAA)组合物的器件更为稳定。
耐四氢呋喃(THF)
为了考察溶剂对组合物的电阻稳定性的影响,将实例1和3的器件悬于盛有25℃的四氢呋喃(THF)的密封玻璃瓶中。定期地把器件从溶剂中取出并揩干。结果表明,含有EBA组合物的器件比含有EAA组合物的器件更稳定。
电阻-温度特性
将实例1和3的器件,每只的电阻为0.029欧姆,插入一只炉中。以每分钟2℃的速率将炉温从20℃升至160℃,并测定电阻。结果如图2所示,该结果表明,含有EBA组合物的器件的峰值电阻为2540欧姆,然而含有EAA组合物的器件的峰值电阻为685欧姆。
表面温度
将实例1和3的器件插入由器件与开关、直流电源、将初始电流限制在10安培的可变电阻器串联而成的电路中。器件在3 VDC(直流伏特)-50VDC范围内的各种不同的电压下突变至高电阻状态。一分钟以后,采用型号为KT19.B2的海曼(Heimann)红外高温计测量了每只器件的表面温度。结果如图3所示,该结果表明,含有EBA组合物的器件在6-50 VDC的范围内保持了108℃的较为稳定的表面温度,然而含有EAA组合物的器件当电压超过20 VDC以后表面温度便急剧升高。
耐电压
将实例1和3的器件插入与开关、直流电源串联的电路中。从10 VDC开始,每次提高20伏特,每通电5秒钟,随即断电60秒钟。当电极断路或者当器件发出电弧并烧坏时,就认为该器件失效了。结果,如图4所示,用这20只试验器件中的失效百分率对外加电压变化作图来表示。含有EBA组合物的器件表现出高达110 VDC的优异完好率统计结果,然而含有EAA组合物的器件的统计结果却显示,其总的完好率很差。
表I
表I注:
实例 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
配方(wt%) | ||||||||||
HDPE | 22.7 | 22.1 | 22.1 | 20.3 | 17.7 | 12.7 | 22.6 | 28.1 | 33.0 | 38.0 |
EAA | 27.6 | |||||||||
EMA | 27.6 | |||||||||
EBA1 | 27.6 | 30.4 | 33.0 | 38.0 | ||||||
EBA2 | 28.1 | 22.6 | 17.7 | 12.7 | ||||||
CB | 50.3 | 50.3 | 50.3 | 49.3 | 49.3 | 49.3 | 49.3 | 49.3 | 49.3 | 49.3 |
比值 | 1.25 | 1.25 | 1.25 | 1.50 | 1.86 | 3.00 | 1.25 | 0.80 | 0.54 | 0.33 |
湿度试验(在85℃/85%湿度下数小时后的Rf/Ri) | ||||||||||
Ri(mΩ) | 21 | 21 | 21 | 47 | 46 | 40 | 40 | 47 | 44 | 44 |
100 | 1.19 | 1.14 | 1.10 | 1.03 | 1.03 | 1.07 | 1.23 | 1.08 | 1.03 | 0.98 |
300 | 1.29 | 1.19 | 1.19 | 0.98 | 0.99 | 1.25 | 1.79 | 1.15 | 0.94 | 0.86 |
500 | 1.48 | 1.19 | 1.29 | |||||||
700 | 2.00 | 1.33 | ||||||||
1000 | 1.38 | |||||||||
1075 | 4.52 | 2.29 | ||||||||
2000 | 2.86 | |||||||||
4225 | 1.21 | 1.28 | 2.13 | 4.35 | 1.51 | 1.00 | 0.93 | |||
耐阻断疲劳(在15 VDC下数小时后的Rf/R | ||||||||||
Ri(mΩ) | 30 | 25 | 41 | 38 | 54 | 49 | 50 | 49 | 35 | |
112 | 5.37 | 2.68 | 1.95 | 1.92 | 2.11 | 3.00 | 2.57 | 2.28 | 1.97 | |
260 | 2.37 | 2.53 | 2.28 | 4.65 | 3.71 | 3.14 | 2.63 | |||
500 | 24.5 | 3.72 | ||||||||
1000 | 48.3 | 6.92 | ||||||||
耐THF(在23℃的THF中数小时后的Rj/Ri) | ||||||||||
Ri(mΩ) | 25 | 23 | ||||||||
12 | 1.70 | 1.53 | ||||||||
23 | 2.49 | 2.04 | ||||||||
40 | 5.34 | 3.12 | ||||||||
88 | 112 | 43 |
HDPE是PetrotheneTMLB832高密度聚乙烯,由Quantum化学公司提供。
EAA是PrimacorTM1320乙烯/丙烯酸共聚物,含有6.5%的丙烯酸,熔体指数为2.5g/10min.,由道化学公司提供。
EMA是EscorTM×S11-04乙烯/丙烯酸甲酯共聚物,含有6.0%的丙烯酸甲酯,熔体指数为6.0g/10min,由埃克森公司提供。
EBA1是EnatheneTM EA 705-009乙烯/丙烯酸正丁酯共聚物,含有5%的丙烯酸正丁酯,熔体指数为3.0g/10min,由Quantum化学公司提供。
EBA2是EnatheneTM EA 719-009乙烯/丙烯酸正丁酯共聚物,含有19%的丙烯酸正丁酯,熔体指数为0.3g/10min.,由Quantum化学公司提供。
CB是RavenTM 430碳黑,由哥伦比亚化学公司提供。
比值是乙烯共聚物对HDPE的重量比。
实例11-21
为了确定聚乙烯与乙烯共聚物形成的共结晶程度,制备了HDPE(PetrotheneTM LB832)、EAA(PrimacorTM 1320)和EBA(EnatheneTMEA 705-009)的数种共混物。在将表II中规定的配料用布拉本德混炼机混炼之后,压塑成块料并切成试样(约7.5毫克)。将每个试样放在精工(Seiko)220C差示扫描量热仪(DSC)中以每分钟10℃的速率从20℃升到200℃(第一加热周期),在200℃下保温10分钟,然后以每分钟10℃的速率降至20℃(第一冷却周期)。在第一组试验中,接着将试样再次以每分钟10℃的速率加热到200℃。将熔融吸热产生的峰值温度记录下来作为组合物的熔点(Tm)。对混合物记录到两个熔点(Tm1和Tm2),各对应于其中一种成分的吸热。另外,记录下HDPE、EAA和EBA对比试样的熔融吸热曲线下方的面积,作为熔融热(Hf),同时还记录下共混物试样的各峰值温度下方的总面积,作为混合物的熔融热。
在第二组试验中,在第二周期时,将那些含有EAA的混合物加热到115℃,而将那些含有EBA的试样加热到120℃,在这两种温度下,EAA和EBA试样分别完全熔融。然后,记录下作为单峰的(即或含EAA,或含EBA)第二加热周期吸热曲线的熔融热数据,然后将它们与采用线性混合规则确定的计算值加以比较。有关线性混合规则、混合物的规则,可参见“混合物性质的预测:科学和工程中的混合规则”,劳伦斯E.尼尔森著(MarcelDekker公司出版,1978)一书的第5-9页,该公开的内容作为参考收入本文。按照这一规则,混合物熔融热的预测值的计算由下式确定:
PB=PHDPE(wt%HDPE)+PCO(wt%乙烯共聚物)其中P代表给定的性质(即熔融热),PB是混合物性质的预测值,PHDPE是第一聚合物(即100%HDPE)性质的测定值,PCO是第二聚合物(即100%乙烯共聚物,或EAA,或EBA)性质的测定值。结果表明,从HDPE/EAA共混物中的EAA成分测得的熔融热计算值与测定值之间的差,比从HDPE/EBA共混物中的EBA测得的对应差值小得多。Hf的计算值和实际值之差的百分率数值示于表II。我们认为,从EBA/HDPE共混物所测得的这种较大的差值反映了EBA与HDPE之间发生了共结晶。有相当数量的EBA与熔点较高的HDPE一起结晶,因而不被包括在120℃以下的熔融吸热曲线里。EAA与HDPE共结晶的程度要小得多,因此,其混合物中的EAA基本上全部在115℃以下就熔融了。图5显示了熔融热随共混物中乙烯共聚物的重量百分数变化的情况。图中还标出了根据混合规则得到的熔融热预测值。
表II
试样 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 |
配方(wt%) | |||||||||||
HDPE | 100 | 0 | 0 | 75 | 45 | 40 | 25 | 75 | 45 | 40 | 25 |
EAA | 0 | 100 | 0 | 25 | 55 | 60 | 75 | 0 | 0 | 0 | 0 |
EBA1 | 0 | 0 | 100 | 0 | 0 | 0 | 0 | 25 | 55 | 60 | 75 |
第一加热周期 | |||||||||||
Tm1(℃) | 101.5 | 105.5 | 100.0 | 100.0 | 100.5 | 100.5 | 103.0 | 102.0 | 102.0 | ||
Tm2(℃) | 131.5 | 132.0 | 130.5 | 131.0 | 130.0 | 130.5 | 131.0 | 128.5 | 129.0 | ||
Hf(J/g) | 197 | 82 | 97 | 167 | 146 | 126 | 114 | 176 | 149 | 147 | 124 |
第二加热周期的第一组试验 | |||||||||||
Tm1(℃) | 102.0 | 105.5 | 100.0 | 99.5 | 100.5 | 101.0 | 103.5 | 102.0 | 103.5 | ||
Tm2(℃) | 135.0 | 135.0 | 133.5 | 134.0 | 133.0 | 133.5 | 133.0 | 130.0 | 130.0 | ||
Hf(J/g) | 214 | 80 | 94 | 1 85 | 148 | 135 | 117 | 185 | 154 | 152 | 121 |
第二加热周期的第二组试验 | |||||||||||
Tm1(℃) | 100.0 | 100.0 | 100.0 | 102.0 | 102.5 | 102.5 | |||||
Hf(J/g) | 34 | 40 | 56 | 18 | 22 | 39 | |||||
Hf计算值(J/g) | 44 | 48 | 60 | 52 | 57 | 71 | |||||
(Hf计算值-Hf)/Hf(%) | 29.4 | 20.0 | 7.1 | 189 | 159 | 82.1 |
Claims (10)
1.一种导电聚合物组合物,其中包含
(A)一种聚合物成分,其中含有
(1)第一聚合物,(a)其含量为该聚合物成分总重量的25-75%,(b)它是聚乙烯,和
(2)第二聚合物,(a)其含量为该聚合物成分总重量的25-75%,(b)它包含由(i)第一单体,即乙烯和(ii)第二单体,即通式为CH2=CHCOOCmH2m+1,其中m至少是4,的丙烯酸烷基酯,衍生而来的单元;以及
(B)一种分散在该聚合物成分中的粒状导电填料。
2.根据权利要求1的组合物,其中第一聚合物是高密度聚乙烯。
3.根据权利要求1或2的组合物,其中m最大是8。
4.根据上述权利要求中任何一项的组合物,其中第二单体是丙烯酸丁酯或丙烯酸异丁酯。
5.根据上述权利要求中任何一项的组合物,其中第二单体的含量为第二聚合物重量的至多20%。
6.根据权利要求1的组合物,其中第二聚合物是含有第三单体的三元共聚物,优选的是,其中该第二单体是丙烯酸丁酯,第三单体是甲基丙烯酸缩水甘油酯。
7.根据上述权利要求中任何一项的组合物,其中导电聚合物组合物表现出PTC行为。
8.根据权利要求1的组合物,其中第二聚合物的含量为聚合物成分重量的30-70%,优选地为聚合物成分重量的35-65%。
9.一种电器件(1),包括
(A)一种由根据权利要求1的导电聚合物组合物构成的元件(3),和
(B)至少一个适合用于将该导电聚合物元件(3)连接到电源上的电极(5)。
10.一种组装件,包括
(A)一种根据权利要求1的电路保护器件(1),和
(B)一种电池,优选的是镍/金属氢化物电池或镍/镉电池,该电池与电路保护器件(1)电气地相连。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/255,497 | 1994-06-08 | ||
US08/255,497 US5582770A (en) | 1994-06-08 | 1994-06-08 | Conductive polymer composition |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1149882A true CN1149882A (zh) | 1997-05-14 |
CN1070889C CN1070889C (zh) | 2001-09-12 |
Family
ID=22968586
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN95193461A Expired - Lifetime CN1070889C (zh) | 1994-06-08 | 1995-06-07 | 导电聚合物组合物 |
Country Status (9)
Country | Link |
---|---|
US (2) | US5582770A (zh) |
EP (1) | EP0764187B1 (zh) |
JP (1) | JP3692141B2 (zh) |
KR (1) | KR970703389A (zh) |
CN (1) | CN1070889C (zh) |
CA (1) | CA2192367A1 (zh) |
DE (1) | DE69522688T2 (zh) |
TW (1) | TW314633B (zh) |
WO (1) | WO1995033792A1 (zh) |
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- 1995-06-07 WO PCT/US1995/007925 patent/WO1995033792A1/en active IP Right Grant
- 1995-06-07 CA CA002192367A patent/CA2192367A1/en not_active Abandoned
- 1995-06-07 US US08/471,876 patent/US5580493A/en not_active Expired - Lifetime
- 1995-06-07 CN CN95193461A patent/CN1070889C/zh not_active Expired - Lifetime
- 1995-06-07 DE DE69522688T patent/DE69522688T2/de not_active Expired - Fee Related
- 1995-06-07 KR KR1019960706997A patent/KR970703389A/ko not_active Application Discontinuation
- 1995-06-07 JP JP50135296A patent/JP3692141B2/ja not_active Expired - Lifetime
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100343925C (zh) * | 2002-03-19 | 2007-10-17 | 热力蒂思科有限公司 | 含有低分子量聚乙烯加工助剂的ptc导电组合物 |
Also Published As
Publication number | Publication date |
---|---|
US5582770A (en) | 1996-12-10 |
DE69522688T2 (de) | 2002-06-20 |
DE69522688D1 (de) | 2001-10-18 |
CN1070889C (zh) | 2001-09-12 |
CA2192367A1 (en) | 1995-12-14 |
KR970703389A (ko) | 1997-07-03 |
JP3692141B2 (ja) | 2005-09-07 |
MX9606206A (es) | 1998-06-30 |
US5580493A (en) | 1996-12-03 |
JPH10501290A (ja) | 1998-02-03 |
WO1995033792A1 (en) | 1995-12-14 |
EP0764187A1 (en) | 1997-03-26 |
EP0764187B1 (en) | 2001-09-12 |
TW314633B (zh) | 1997-09-01 |
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