CN1353424A - 通过温度自动调节电阻的导电聚合物复合材料 - Google Patents
通过温度自动调节电阻的导电聚合物复合材料 Download PDFInfo
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- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
本发明涉及一种复合材料,以总重量100%计,包含如下组份:A)40-90%基本呈β形式结晶的PVDF均聚物或共聚物,B)10-60%导电填料,C)0-40%结晶或半结晶聚合物,D)0-40%除C以外的填料,结果是,呈β形式的结晶在导电填料颗粒的表面上成核。该材料是通过温度自动控制电阻的导体。导体显示出随温度而电阻增加(PTC或“正温系数效应”),以致使强度稳定在均衡温度。
Description
[发明领域]
本发明涉及一种通过温度自动调节电阻的导电聚合复合材料。更准确地说,本发明涉及一种包含导体,如炭黑或任何其它导电材料的含氟聚合物。
通过在聚合物基体中掺入石墨,可能使复合物导电。施加足够的电压将通过焦耳效应产生热量。在不存在电路断路开关机理时,温度将一直升高至材料被损坏为止。本发明的材料基于含氟聚合物,所述氟聚合物包含作为填料的导体,如石墨,其显示出随温度而电阻增加(为温度的函数)(PTC或“正温系数”效应),以致使在平衡温度时强度稳定。因此,该PTC效应使之可能对电流强度进行热控制。与常规电阻相比,它显示出许多优点:
·电加热体系的控制通常通过电路中包括热断路开关而获得。在断路开关失败的情况下,电路或安全保险丝熔断。PTC材料是自动控制的,既不需要包括断路开关也不需要保险丝。
·PTC加热体系具有降低燃烧和短路的危险。
·在PTC加热元件区偶然接地的情况下,不会发生短路。
·PTC效应将产生适当的温度,当与常规体系相比时这将在两个方面有益处:
在更为广泛的表面区域传入热量。
·复合材料能够通过塑料工业中使用的方法而转换(共挤塑,模塑等)。它也能够以涂料的形式涂至绝缘材料上,无论其几何构形如何。[现有技术及技术问题]
现有技术披露了两种具有PTC效应的复合聚合物体系。
根据第一种体系,PTC效应基于:中断导电填料网络的聚合物结晶的膨胀现象。当炭黑在半结晶聚合物基体中的含量增加至电阻下降的浓度时,复合材料的电阻将慢慢降低。后者表示称之为渗滤阈(Seuil de Percolation)的几何转换。业已发现,PTC效应的最大值相当于根据渗滤阈发现的临界浓度。当材料的温度接近基体的熔融温度时,结晶区的膨胀将引起PTC效应。然而,炭黑颗粒的高能量和基体的低剪切模量将使电阻下降,这被称为NTC效应(负温系数)。第一类体系描述于下列参考文献中(CA表示化学文摘):
131:243891 CA
题目(IT) 具有高转换温度的有机PTC热敏电阻材料作者(AU) Yang,Fubiao;Li,Yongqin;Li,Xiaojun机构(CS) 国防科技大学5系,中国长沙410073
(Department 5,National University of Defense Technology,Changsha,
410073,Peop.Rep.China)来源(SO) 功能材料(Gongneng Cailiao)(1998),29(Suppl.),724-725CODEN:GOCAEA;ISSN:1001-9731出版(PB) 功能材料编辑部(Gongneng Cailiao Bianjibu)
129:331461 CA
题目 热处理对导电PVDF/CB复合材料结晶和PTC性能的影响作者 Wang,Jikui;Wang,Gengchao;Zhang,Bingyu;Fang,Bin;Zhang,Zhiping机构 华东科技大学材料科学工程学院,中国上海2000237
(Inst.Mater.Sci.Eng.,East China Univ.Sci.Technol.,Shanghai,200237,
Peop.Rep.China)来源 高分子材料科学与工程(Gaofenzi Cailiao Kexue Yu Gongcheng)
(1998),14(5),93-95
CODEN:GCKGEI;ISSN:1000-7555出版 “高分子材料与工程”编辑部
("Gaofenzi Cailiao Kexue Yu Gongcheng"Bianjibu)
125:277325 CA
题目 结晶过程对PVDF/CB复合材料的PTC/NTC效应的影响作者 Zhang,Mingyin;Jia,Wentao;Chen,Xinfang机构 吉林大学材料科学系,中国长春 130023
(Dep.Materials Science,Jilin Univ.,Changchun,130023,Peop.Rep.China)来源 聚合物应用科学杂志(J.Appl.Polym.Sci.)(1996),62(5),743-747
CODEN:JAPNAB;ISSN:0021-8995
104:121274 CA
题目 加热器
IN Shibata,Tsuneo;Nishida,Takeo;Terakado,Masayuki;Nitta,Isao
PA Matsushita Electric Industrial Co.,Ltd.,Japan
SO Jpn.Tokkyo Koho,5 pp.
CODEN:JAXXAD
根据第二种复合聚合物体系,PTC效应基于:两种可混溶聚合物的存在。在这种材料中,包含炭黑作为填料的PVDF/HDPE体系是最为熟知的。PVDF和HDPE相可混溶并因此在这种情况下的PTC效应主要取决于形态和在所述两相之间炭黑的分布。炭黑优选分散在HDPE相中,该相将变成导电相。如果PVDF相对于HDPE处于良好均衡态的话,PVDF相将形成有利于PTC效应的特定结构。导电PE相在PVDF相中独特的分布是阻挠NTC效应的条件,NTC效应在HDPE熔点时产生,该熔点低于PVDF的熔点。第二体系描述于下列参考文献中:
131:287163 CA
题目 炭黑填充的聚(偏二氟乙烯)和高密度聚乙烯的可混溶掺混物:形态和正温系数效应及负温系数效应之间的关系作者 Feng,Jiyun;Chan,Chi-Ming机构 香港科技大学化学工程高级工程材料设备系,香港Kowloon
(Department of Chemical Engineering Advanced Engineering Materials
Facility,The Hong Kong University of Science and Technology,Kowloon,
Hong Kong)来源 聚合工程科学(Polym.Eng.Sci.)(1999),39(7),1207-1215
CODEN:PYESAZ;ISSN:0032-3888出版 塑料工程师协会(Society of Plastics Engineers)
130:96227 CA
题目 炭黑填充的聚(偏二氟乙烯)和高密度聚乙烯的可混溶掺混物:电性能和形态作者 Feng,Jeng;Chan,Chi-Ming机构 香港科技大学化学工程高级工程材料设备系,香港Kowloon
(Dep.of Chemical Engineering,Advanced Engineering Materials Facility,The Hong Kong University of Science and Technology,Kowloon,Hong Kong)来源 聚合工程科学(Polym.Eng.Sci.)(1998),38(10),1649-1657
CODEN:PYESAZ;ISSN:0032-3888出版 塑料工程师协会(Society of Plastics Engineers)
130:52964 CA
题目 炭黑填充的聚(偏二氟乙烯)和高密度聚乙烯的可混溶掺混物:电性能和形态作者 Feng,Jiyun;Chan,Chi-Ming机构 香港科技大学化学工程高级工程材料设备系,香港Kowloon
(Department of Chemical Engineering,The Hong Kong University ofScience and Technology,Kowloon,Hong Kong)来源 年度技术会议-塑料工程师协会(Annu.Tech.Conf.-Soc.Plast.Eng.)
(1998),56th(Vol.2),2476-2480CODEN:ACPED4;ISSN:0272-5223出版 塑料工程师协会(Society of Plastics Engineers)
以及专利申请WO9805503。
现已发现,由(i)基本呈β形式结晶的PVDF均聚物或共聚物的掺混物和(ii)导电填料组成的复合材料、使得以β形式的结晶在导电填料颗粒的表面上成核,显示出PTC效应,但其机理与现有技术不同。
用于复合材料中PVDF以β形式(或I型)结晶。这是一种压电极性结晶排列,其结晶能够在电场方向上取向并有助于电荷的传递。例如,关于PVDF共聚物(VF2,HFP和TFE),当富含在HFP和TFE单元中的结晶的表面通过熔融而扰乱时,该形态排列将由于温度而遭到破坏,导电填料颗粒之间的电荷转移将减慢且电阻将增加,这将通过PTC效应而反映出。
[发明概述]
本发明涉及一种复合材料,以总重量100%计,包含如下组份:
A)40-90%基本呈β型结晶的PVDF均聚物或共聚物,
B)10-60%导电填料,
C)0-40%结晶或半结晶聚合物,
D)0-40%除C以外的填料,
结果是,呈β型的结晶在导电填料颗粒的表面上成核。
对于利用温度自动控制的“加热”应用,基于所用聚合物的压电性能,显示出本发明PTC效应的材料,相对于已描述的材料而言,具有许多优点:
·在我们的体系中,电阻也取决于导电填料的浓度,然而它并不局限于临界浓度;因此,PTC效应在很宽的电阻范围内被观察到。因此,这使之可能通过导电填料的含量调节:用于获得焦耳效应的电压值,它是通过PTC效应良好进行温度自动控制所必需的。
·本发明材料在玻璃化转移温度(约-30℃)至熔融温度(95-165℃,根据本发明配方)的宽温度范围内具有PTC效应,而对于现有技术的材料,进行控制的温度范围被限制在结晶区的熔融温度。因此,明显地改进了材料的PTC效应,这使之可能在低于熔融温度的大温度范围内获得并控制所希望的温度。
·PTC/NTC效应的峰比现有技术体系PTC/NTC效应的峰要窄得多。通过在更低温度下更好的自动控制,本发明的复合材料将具有更小的超过该峰值温度并因此产生过热的危险。
·本发明的材料在过热之后将再生其形态,而对于现有技术的复合材料而言,可逆性是偶然的。
·所提出的复合材料易溶解于常用的溶剂中。由所述溶液或熔体制备的材料具有相同的性能,而用于现有技术复合材料中的聚合物很难溶解。
本发明的材料以沉积至绝缘基材如陶瓷、玻璃、纺织纤维、织物和任何绝缘区域上的涂层的形式来施加,为了制备所述材料,将将导电填料(B)充分分散于聚合物(A)中,其或者呈熔融态或者为适当溶剂如丙酮或N-甲基吡咯烷酮中的溶液。包含填料(B)和可有可无(C)和(D)的聚合物(A)以涂料的涂覆至绝缘表面(优选陶瓷)上,其或者呈熔融态或者为适当溶剂中的溶液。在涂覆之前或之后,能够将连接至电路的金属端设置在涂层的两端。在使熔融聚合物冷却之后或在为了除去溶剂的干燥之后,准备加热元件。
在电流i通过期间形成加热。根据焦耳效应,在时间t期间放出的热量W为:
W=Ri2t
该公式表明在体系的电阻为在施加电压下电流强度是充分的条件下,能够提供有效的加热。通过改变聚合物/导电填料的比例而实现有效加热的最佳化。
宏观上,以包含填料(B)的聚合物(A)的基体的形式提供复合材料。例如,如果(A)是包含石墨作为填料的偏二氟乙烯(VF2),四氟乙烯(TFE)和六氟丙烯(HFP)的共聚物(Kynar9301),那么,宏观上,以包含石墨作为填料的该共聚物的基体提供复合材料。在石墨颗粒之间的空间被β型结晶(反-反-反极性结构)和HFP及TFP单元组成的非晶形区之间划分。为了升高控制区的上限,可加入一定量的PVDF(至多40%)或其与三氟乙烯或四氟乙烯的共聚物,前提条件是,VF2的质子以β型结晶的形式进行结晶。所述组合物可包含(C)和/或(D),以便改善机械性能。[发明详述]
关于聚合物(A),更准确地说共聚物,有利的是,其共聚单体选自这样的化合物,所述化合物包含能够打开以便进行聚合的乙烯基并且包含直接连接至该乙烯基上的至少一个氟原子,一个氟烷基或一个氟烷氧基。
作为共聚单体的例子,可以提及的有:氟乙烯;三氟乙烯(VF3);氯三氟乙烯(CTFE);1,2-二氟乙烯;四氟乙烯(TFE);六氟丙烯(HFP);全氟(烷基乙烯基)醚、如全氟(甲基乙烯基)醚(PMVE),全氟(乙基乙烯基)醚(PEVE)和全氟(丙基乙烯基)醚(PPVE);全氟(1,3-间二氧杂环戊烯);全氟(2,2-二甲基-1,3-间二氧杂环戊烯)(PDD);结构式CF2=CFOCF2CF(CF3)OCF2CF2X的产品,式中X为SO2F,CO2H,CH2OH,CH2OCN或CH2OPO3H;结构式CF2=CFOCF2CF2SO2F的产品;结构式F(CF2)nCH2OCF=CF2,式中n为1,2,3,4或5;结构式R1CH2OCF=CF2的产品,式中R1为氢或F(CF2)z,z为1,2,3或4;结构式R3OCF-CH2的产品,式中R3为F(CF2)z-,z为1,2,3或4;(全氟丁基)乙烯(PFBE);3,3,3-三氟丙烯和2-三氟甲基-3,3,3-三氟-1-丙烯。可以使用若干个共聚单体。
复合材料中的聚合物(A)结晶成β形式,这是由于聚合物(A)在与导电填料(B)混合之前已呈β形式,或者由于在复合材料制备期间,它以该β形式进行结晶。例如,当使溶剂蒸发时,没有任何填料、溶解于溶剂中的PVDF共聚物以β形式进行结晶。根据另一方法,在热处理以及慢慢冷却之后,存在填料(B)的PVDF均聚物或共聚物基本上以β形式结晶。如果聚合物(A)不是完全地以β形式进行结晶,但β形式的比例必须足以产生PTC效应,那么这也不脱离本发明的范围。有利的是,聚合物(A)中β形式的比例必须至少为60%,优选为75%。压电结晶相的存在不是获得PTC效应的唯一条件。β形式(或I形式)的结晶必须在导电填料、如石墨的颗粒表面上成核。
作为聚合物(A)的例子,可以提及的有:具有任何缺陷水平(也使用术语“反转缺陷(défaut de retournement)”或“反转度”)的PVDF均聚物。术语反转缺陷应当理解为:沿聚合物链-CH2-CF2-CF2-CH2-型的任何组合(也称之为头-头组合,这与-CH2-CF2-CH2-CF2-型的头-尾组合相反)。缺陷的水平可利用氟的RMN(核磁共振)来测量;因此,反转缺陷水平通常以百分比的形式给出。
另外,还可以提及的是:VF2和VF3的共聚物,其中VF2的含量至少为60%摩尔,有利的是至少75%摩尔;或VF2,TFE和HFP的共聚物,其中TFE的含量至少为15%摩尔;有利的是,VF2-TFE-HFP共聚物,其中各摩尔组分为60-85/15-20/0-25。
关于导电填料(B),可以选自由导电材料组成的任何粉末,有利的是金属粉末,炭黑,石墨和金属氧化物,如在FR2774100中引证的那些粉末。通过改进(B)和(A)的比例以及在恒定的电压下,可能改进由PTC效应所获得的温度。所述温度可在熔化温度和-50℃之间,有利的是在-20℃和130℃之间。(B)的比例越大,温度将越高。
关于聚合物(C),它是不干扰聚合物(A)结晶的任何聚合物。作为例子,可以提及的是:不呈β形式结晶的PVDF均聚物和至少含85% VF2有利地至少含90% VF2的VF2-HFP的共聚物。
关于填料(D),可以提及的是:用于含氟聚合物的常用填料,如二氧化硅,PMMA或抗紫外剂。
本发明的复合材料可以根据两种方法进行制备。根据第一种方法,将各组份(A),(B)和可有可无的(C)和/或(D)复合,以致使(A)处于熔融状态,然后将得到的产品施加至绝缘表面上。可以使用用于使热塑性聚合物混合的常用装置,如混合器或挤出机。在所述混合操作结束后,以颗粒的形式,对获得的产品进行冷却并贮存,然后对其进行加热以使之熔融,并将其施加至绝缘表面上,这也没有脱离本发明的范围。
根据第二种方法,将各组份(A),(B)和可有可无的(C)和/或(D)置于溶剂中,直至得到浓分散体为止,然后以涂料的形式将该分散体施加至绝缘材料的表面上。所述溶剂选自丙酮,异佛尔酮,二甲基甲酰胺(DMF),甲乙酮(MEK)和N-甲基吡咯烷酮(NMP)。
例如,通过将(A)和(B)掺混,然后将整个的混合物和可有可无的(C)和/或(D)溶解于溶剂,而采用这两种方法结合。
另外,本发明还涉及包含上述复合材料的加热装置。
[实施例]
实施例1
当将下列配方(以重量计)施加在通过10厘米分开的两端之间并置于110V的电压下时,将得到良好的加热控制。
Kynar9301-52%
石墨9000(约5-10微米的颗粒)-48%
将100份上述的组合物溶解于30份丙酮中。
Kynar9301表示VF2-TFE-HFP共聚物,其各自的摩尔比例为72/18/10,
石墨9000表示约5-10微米的颗粒。
将掺混物施加至10×10cm的陶瓷板上。将两个金属电线放置于薄膜上,以便随后用作电极。在60℃干燥1小时之后,当通过外部加热而使温度升高时,薄膜的电阻将增加。结果记录在图1中。在110V的电压下,通过焦耳效应对涂层进行加热,随着温度增加其强度将下降。结果记录在图2中。
实施例2
制备Kynar9301和石墨9000的掺混物。将这些掺混物溶解于溶剂中,然后在室温进行干燥。结果记录在下表1中。
表1
%B(石墨) | 溶剂 | 厚度mm | 触点/宽度之间的距离,mm | R,Ohm | U,V | T℃ | I,mA |
50 | MEK | 0.1 | 60/70 | 43 | 38 | 70 | |
45 | MEK | 0.1 | 80/60 | 75 | 43 | 50 | 266 |
40 | MEK | 0.06 | 90/70 | 180 | 50 | 50 | |
35 | MEK | 0.06 | 90/70 | 640 | 60 | 50 | |
30 | MEK | 0.05 | 75/65 | 350 | 60 | 50 | 125 |
25 | MEK | 0.045 | 80/60 | 980 | 67 | 50 | 60 |
40 | 丙酮 | 0.085 | 90/70 | 114 | 40 | 50 | 223 |
35 | 丙酮 | 0.055 | 90/65 | 315 | 70 | 50 | 16 |
30 | 丙酮 | 0.045 | 85/65 | 325 | 75 | 50 | 15 |
20 | 丙酮 | 0.1 | 70/80 | 530 | 120 | 50 | 16 |
15 | 丙酮 | 0.1 | 70/80 | 1337 | 210 | 44 | 5 |
10 | 丙酮 | 0.1 | 70/80 | 15200 | 210 | 35.5 | 2.4 |
业已发现,通过改变电压或改进聚合物/石墨的比例或通过几何构形(两端之间的厚度或距离),能够获得希望的温度(例如50℃)。
实施例3
以PVDF均聚物(KYNAR500)于DMF中7%的溶液为基础,通过添加25%(相对于PVDF)的石墨而制备涂料。对10×10cm的陶瓷板进行涂布并将两个铜接头粘接至表面的两端。在120℃对涂层干燥4小时,然后,在170℃退火30分钟,并冷却至室温。
在测试之前,将陶瓷板贮存2个月。电阻为837欧姆,厚度约为50微米。
将150V的交流电压施加至接线柱上,并监测温度的改变。在约30分钟之后,温度稳定在84℃,并且经5天的时间,慢慢增加至91℃,然后保持恒定(±1℃)2个月。在该试验之后,所述板的电阻将稍稍下降(750欧姆)。
在相同电压并且仍保留在相同温度(91±1℃)下,将板放置若干天。
该试验表明了Kynar 500/石墨加热涂料很好的性能。
Claims (6)
1.一种复合材料,以总重量100%计,包含如下组份:
A)40-90%基本呈β形式结晶的PVDF均聚物或共聚物,
B)10-60%导电填料,
C)0-40%结晶或半结晶聚合物,
D)0-40%除C以外的填料,
结果是,呈β形式的结晶在导电填料颗粒的表面上成核。
2.根据权利要求1的材料,其中(A)选自VF2和VF3的共聚物,其中至少有60%摩尔的VF2。
3.根据权利要求1的材料,其中(A)选自VF2,TFE和HFP的共聚物,其中至少有15%摩尔的TFE单元。
4.根据权利要求3的材料,其中(A)选自VF2-TFE-HFP的共聚物,其中各摩尔组分为60-80/15-20/0-25。
5.根据前述任一项权利要求的材料,其中(C)选自不呈β形式的PVDF均聚物,和含至少85%VF2的VF2-HFP的共聚物。
6.一种包含前述任一项权利要求的复合材料的加热装置。
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FR01/02264 | 2001-02-20 | ||
FR0102264A FR2816626A1 (fr) | 2000-11-13 | 2001-02-20 | Materiau composite polymerique conducteur a resistance auto-controlee par la temperature |
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JPS60168742A (ja) * | 1984-02-10 | 1985-09-02 | Mitsubishi Petrochem Co Ltd | 溶融成形体 |
JPS6122590A (ja) * | 1984-07-10 | 1986-01-31 | ダイキン工業株式会社 | 高分子複合発熱体 |
US5093036A (en) * | 1988-09-20 | 1992-03-03 | Raychem Corporation | Conductive polymer composition |
US5451919A (en) * | 1993-06-29 | 1995-09-19 | Raychem Corporation | Electrical device comprising a conductive polymer composition |
JPH0967462A (ja) * | 1995-08-31 | 1997-03-11 | Tdk Corp | 正の温度特性を持つ有機抵抗体 |
-
2001
- 2001-02-20 FR FR0102264A patent/FR2816626A1/fr active Pending
- 2001-10-24 EP EP20010402755 patent/EP1205514A1/fr not_active Withdrawn
- 2001-11-08 US US09/986,448 patent/US20020094441A1/en not_active Abandoned
- 2001-11-09 KR KR10-2001-0069723A patent/KR100454769B1/ko not_active IP Right Cessation
- 2001-11-13 CN CN01137422A patent/CN1353424A/zh active Pending
- 2001-11-13 JP JP2001347929A patent/JP2002206040A/ja active Pending
- 2001-11-13 CA CA 2363332 patent/CA2363332A1/fr not_active Abandoned
-
2003
- 2003-06-30 US US10/608,149 patent/US6790530B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101606432B (zh) * | 2007-02-19 | 2012-02-01 | 罗姆股份有限公司 | 加热器 |
Also Published As
Publication number | Publication date |
---|---|
US20020094441A1 (en) | 2002-07-18 |
EP1205514A1 (fr) | 2002-05-15 |
US6790530B2 (en) | 2004-09-14 |
FR2816626A1 (fr) | 2002-05-17 |
KR20020037273A (ko) | 2002-05-18 |
CA2363332A1 (fr) | 2002-05-13 |
US20040001954A1 (en) | 2004-01-01 |
JP2002206040A (ja) | 2002-07-26 |
KR100454769B1 (ko) | 2004-11-05 |
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