CN100365080C - 基于pvdf的ptc涂料及其在自我调节加热体系的应用 - Google Patents
基于pvdf的ptc涂料及其在自我调节加热体系的应用 Download PDFInfo
- Publication number
- CN100365080C CN100365080C CNB2004100794318A CN200410079431A CN100365080C CN 100365080 C CN100365080 C CN 100365080C CN B2004100794318 A CNB2004100794318 A CN B2004100794318A CN 200410079431 A CN200410079431 A CN 200410079431A CN 100365080 C CN100365080 C CN 100365080C
- Authority
- CN
- China
- Prior art keywords
- composition
- vinylidene fluoride
- pvdf
- poly
- graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 89
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- 239000000203 mixture Substances 0.000 claims abstract description 57
- 239000011248 coating agent Substances 0.000 claims abstract description 41
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 38
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- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000011231 conductive filler Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 35
- -1 poly(vinylidene fluoride) Polymers 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 229910002804 graphite Inorganic materials 0.000 claims description 26
- 239000010439 graphite Substances 0.000 claims description 26
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 25
- 229920001519 homopolymer Polymers 0.000 claims description 21
- 230000005855 radiation Effects 0.000 claims description 15
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 15
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
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- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 5
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 4
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
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- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
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- 239000004416 thermosoftening plastic Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 229920006370 Kynar Polymers 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明涉及一种组合物,以总重量100%计,包含如下组分:A)40—80%PVDF;B)10—40%PMMA;和C)10—40%导电填料。该组合物具有PTC效应并且有利地以覆盖基材的膜(涂料)的形式使用。将本发明的组合物溶于溶剂中,随后遍布于基材上,并且蒸发掉溶剂。在涂敷之前或之后,可将连接电路的金属端设置在涂层的末端。本发明还涉及一种复合材料,即是涂敷了上述PTC组合物的基材。
Description
技术领域
本发明涉及一种具有温度方式(temperature-wise)自我调节电阻(self-regulated resistance)的导电涂料。更具体地说,本发明涉及一种基于PVDF(聚偏1,1-二氟乙烯)或PMMA的涂料,并且该涂料包含导体,比如炭黑或任何其它电导体。
通过掺入石墨,可能使聚合物材料导电。施加足够高的电压将通过焦耳效应(Joule effect)使材料升温。在不存在断路器装置时,温度将一直升高至材料被损坏为止。本发明的涂料显示出作为温度函数而电阻增加(正温度系数或PTC效应),从而使电流在平衡温度下稳定。因而,该PTC效应使得电流强度受温度调节-与常规的电阻器相比,它显示出很多优点。电加热体系通常通过电路中的热断流器(thermal cut-out)调节。如果热断流器发生故障,电路或安全保险丝则会熔断。PTC材料可自我调节而不必含有断流器或保险丝。
背景技术
专利申请EP1205514公开了一种复合材料,以总重量100%计,包含:
40-90%基本呈β型结晶的PVDF均聚物或共聚物;
10-60%导电填料;
0-40%结晶或半结晶聚合物;
0-40%除了上述结晶或半结晶聚合物以外的填料;
并且使得这些晶体以β-型在导电填料颗粒的表面上成核。
这种材料可用作涂层沉积于绝缘基材如陶瓷、玻璃、木材、纺织纤维(textile fiber)、织品或任何绝缘表面上。为了制备该涂层,所需的是将导电填料分散于PVDF中,PVDF或者呈熔融态或者是溶于适当溶剂比如丙酮或N-甲基吡咯烷酮中的溶液。熔融的或溶解在溶剂中的PVDF可作为涂料涂布于绝缘表面上,该PVDF含有导电填料和任选的结晶聚合物和其它填料。在涂布之前或之后,可将连接电路的金属端设置在涂层的末端。在冷却熔融聚合物之后或在为了除去溶剂的干燥之后,准备加热元件。
关于不同于结晶或半结晶聚合物的填料,该说明书提到“...用于合氟聚合物的常用填料,比如硅石,PMMA,紫外稳定剂等”。
现已发现PMMA是必需组分并且它不是与硅石或紫外稳定剂同样意义的简单填料。还已经发现PVDF可以是任何晶体形式。
发明内容
本发明涉及一种组合物,以总重量100%计,包含:
A)40-80%(有利地50-80%)PVDF;
B)10-40%PMMA;和
C)10-40%导电填料。
该组合物具有PTC效应并且有利地以覆盖基材的膜(涂料)的形式应用。
将本发明的组合物溶于溶剂中,随后遍布于基材上,并且蒸发掉溶剂。在涂敷之前或之后,可将连接电路的金属端设置在涂层的末端。
由PVDF的半结晶结构产生的PTC效应可使得PVDF能进行温度自我调节。基于PVDF、PMMA和导电填料(薄片状石墨和/或炭黑)的本发明组合物提供了具有更高性能和更好安全操作性的材料。PMMA的存在降低了PVDF的结晶度,并且可获得更好的体系凝聚力和更好的涂料粘附力。
本发明还涉及一种复合材料,即是完全或部分覆盖了上述PTC组合物的基材。
关于PVDF,该术语是指VDF(1,1-二氟乙烯,有时也称为VF2)均聚物和VDF共聚物二者。术语“VDF共聚物”是指基于VDF和至少一种其它氟化单体的聚合物。有利的是,氟化共聚单体选自含有能打开以便聚合的乙烯基以及含有直接连接至该乙烯基的至少一个氟原子、氟代烷基或氟代烷氧基的化合物。
作为共聚单体的例子,可以提及的是氟乙烯;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);式CF2=CFOCF2CF(CF3)OCF2CF2X的产品,其中X是SO2F,CO2H,CH2OH,CH2OCN或CH2OPO3H;式CF2=CFOCF2CF2SO2F的产品;式F(CF2)nCH2OCF=CF2的产品,其中n是1,2,3,4或5;式R1CH2OCF=CF2的产品,其中R1是氢或F(CF2)z且z是1,2,3或4;式R3OCF=CH2的产品,其中R3是F(CF2)z-且z是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。可使用多种共聚单体。
可以提及的是VDF/VF3共聚物,其含有至少60mol%,有利地至少75mol%并且优选至少85mol%VDF。
还可以提及的是VDF/TFE/HFP共聚物,其含有至少15mol%TFE单元并且有利地,各摩尔组成为60-80/15-20/0-25(总和为100)的VDF/TFE/HFP共聚物。
还可以提及的是,优选含有至少60重量%VDF的1,1-二氟乙烯(VDF)共聚物,共聚单体选自氯三氟乙烯(CTFE),六氟丙烯(HFP),三氟乙烯(VF3)和四氟乙烯(TFE)。有利地,VDF的比例至少为75%并优选至少为85%。在上述共聚单体中,优选HFP。
有利的是,PVDF(A)是(A1)和(A2)的共混物,其中(A1)选自PVDF均聚物和含有至少85重量%VDF的VDF/HFP共聚物,(A2)是VDF/TFE/HFP共聚物,其含有至少15mol%TFE单元并且有利地,VDF/TFE/HFP共聚物的各摩尔组成为60-80/15-20/0-25(总和为100)。以重量计,(A1)和(A2)的比例(A1)/(A2)可以为20/80-80/20。
PVDF可被部分或全部改性,也即是说为了提高涂料和基材之间的粘合力,可引入官能团。有利的是,改性的PVDF选自:
-接枝了不饱和单体的PVDF,在无氧的情况下,通过辐射共混物进行接枝;
-在有氧下辐射的PVDF(这也称作氧化的PVDF1);和
-脱氟化氢并随后氧化的PVDF(也称作氧化的PVDF2)。
有利的是,所需的是改性PVDF(A)的一部分,该部分可为(A)的0.5-30%重量。优选,是PVDF(A1)被全部或部分改性。
现在将描述改性的PVDF。它们可通过上述PVDF制得。
对于接枝的PVDF,它们可通过在PVDF上接枝不饱和单体的方法制得,其中:
a)含氟聚合物与不饱和单体熔融共混;
b)将a)获得的共混物制成薄膜,片材,颗粒或粉末;
c)在不存在空气下,从b)步骤获得的产品受到1-15Mrad剂量的光子(γ)或电子(β)辐射;以及
d)为了除去未接枝于含氟聚合物上的全部或某些不饱和单体,任选对c)步骤获得的产品进行处理。
对于不饱和接枝单体,可提及的例子是羧酸和它们的衍生物,酰氯,异氰酸酯,唑啉,环氧化物,胺和氢氧化物。不饱和羧酸的例子是具有2-20个碳原子的羧酸,比如丙烯酸,甲基丙烯酸,马来酸,反丁烯二酸和衣康酸。这些酸的官能衍生物包括例如不饱和羧酸的酸酐,酯衍生物,酰胺衍生物,酰亚胺衍生物和金属盐(比如碱金属盐)。还可以是十一碳烯酸。尤其优选的接枝单体是具有4-10个碳原子的不饱和二羧酸以及它们的官能衍生物,具体地它们的酸酐。这些接枝单体包括例如马来酸,反丁烯二酸,衣康酸,柠康酸,烯丙基琥珀酸,环己-4-烯-1,2-二羧酸,4-甲基环己-4-烯-1,2-二羧酸,二环[2.2.1]庚-5-烯-2,3-二羧酸和x-甲基二环[2.2.1]庚-5-烯-2,3-二羧酸以及马来酸酐,衣康酸酐,柠康酸酐,烯丙基琥珀酸酐,环己-4-烯-1,2-二羧酸酐,4-亚甲基环己-4-烯-1,2-二羧酸酐,二环[2.2.1]庚-5-烯-2,3-二羧酸酐和x-甲基二环[2.2.1]庚-5-烯-2,2-二羧酸。
其它接枝单体的例子包括不饱和羧酸的C1-C8烷基酯或缩水甘油酯衍生物,比如丙烯酸甲酯,甲基丙烯酸甲酯,丙烯酸乙酯,甲基丙烯酸乙酯,丙烯酸丁酯,甲基丙烯酸丁酯,丙烯酸缩水甘油酯,甲基丙烯酸缩水甘油酯,马来酸单乙酯,马来酸二乙酯,反丁烯二酸单甲酯,反丁烯二酸二甲酯,衣康酸单甲酯和衣康酸二乙酯;不饱和羧酸的酰胺衍生物,比如丙烯酰胺,甲基丙烯酰胺,马来酸单酰胺,马来酸二酰胺,马来酸的N-单乙基酰胺,马来酸的N,N-二乙基酰胺,马来酸的N-单丁基酰胺,马来酸的N,N-二丁基酰胺,反丁烯二酸单酰胺,反丁烯二酸二酰胺,反丁烯二酸的N-单乙基酰胺,反丁烯二酸的N,N-二乙基酰胺,反丁烯二酸的N-单丁基酰胺,反丁烯二酸的N,N-二丁基酰胺;不饱和羧酸的酰亚胺衍生物,比如马来酰亚胺,N-丁基马来酰亚胺和N-苯基马来酰亚胺;和不饱和羧酸的金属盐,比如丙烯酸钠,甲基丙烯酸钠,丙烯酸钾和甲基丙烯酸钾。
有利的是,使用马来酸酐。
步骤a)可在任何混合装置中进行,比如在热塑塑料工业中使用的挤压机或搅拌机。
对于PVDF和不饱和单体的比例,有利地,以重量计,相应每0.1-10%不饱和单体,PVDF的比例是90-99.9%。优选,相应每0.1-5%不饱和单体,PVDF的比例是95-99.9%。
发现在步骤a)之后,PVDF和不饱和单体的混合物损失了约10-50%在步骤a)开始时掺入的不饱和单体。这一比例取决于不饱和单体的挥发性和本性。实际上,单体在挤压机或搅拌机中被放出并可从通风回路回收。
对于步骤c),有利的是,将步骤b)之后回收得到的产品包裹于聚乙烯袋中,排出空气后密封袋子。对于辐射方法没有限制,可使用电子辐射,更通常称作β辐射,和光子辐射,更通常称作γ辐射。有利的是,剂量在2-6Mrad之间并且优选在3-5Mrad之间。
对于步骤d),可通过任何方式除去未接枝的单体。相对于步骤c)开始时存在的单体量,接枝单体的比例在50-100%之间。产品可用对PVDF和接枝官能团惰性的溶剂洗涤。例如,当与马来酸酐接枝时,可用氯苯洗涤产物。更简单地,还可以对步骤c)回收得到的产品进行真空脱气。
对于氧化的PVDF1,它们可通过氧化含氟聚合物的方法制备,其中:
a)将PVDF制成薄膜,薄片,颗粒或粉末;
b)在有氧下,对a)步骤获得的产品进行1-15Mrad剂量的光子(γ)或电子(β)辐射;以及
c)为了除去全部或某些副产物杂质,任选对b)步骤获得的产品进行处理。
对于辐射和首先步骤a),产品有利地包裹于聚乙烯袋中并且聚乙烯袋是未惰性化的。有利的是,PVDF是粉末状的。聚乙烯袋除了聚乙烯层外还可以包含铝层。在纯氧气存在的情况下辐射是不必要的,仅需要存在氧气。辐射可在含有氧气的惰性气体中进行。术语“惰性气体”是指不参与辐射反应或不参与通过氧气对含氟聚合物改性的气体。有利的是,以体积计,相应于每99-80%惰性气体,氧气的比例是1-20%。有利的是,辐射在空气中进行。对于步骤b)中的辐射方法没有限制,可使用电子辐射,更常称作β辐射,和光子辐射,更常称作γ辐射。有利的是,剂量在2-12Mrad之间并且优选在2-8Mrad之间。
对于步骤c),可通过任何方式除去杂质。产品可用对氧化的PVDF惰性的溶剂洗涤。更简单地,还可以对步骤b)回收得到的产品进行真空脱气。
对于氧化的PVDF2,它们可通过专利EP1054023所公开的方法制备。它公开了一种化学改性含氟聚合物的方法,其特征在于将其部分脱氟化氢并随后使其与氧化剂接触,尤其是过氧化氢或次氯酸盐。
对于PMMA,它是指甲基丙烯酸甲酯均聚物以及含有至少50重量%甲基丙烯酸甲酯的共聚物。作为共聚单体的例子,可以提及的是,例如(甲基)丙烯酸烷基酯,丙烯腈,丁二烯,苯乙烯和异戊二烯。(甲基)丙烯酸烷基酯的例子描述于Kirk-Othmer,Encyclopedia of chemical technology,第4版第1卷292-293页和第16卷475-478页。有利的是,以重量计,PMMA可含有0-20%并优选5-15%的至少一种其它的(甲基)丙烯酸烷基酯,如丙烯酸甲酯和/或丙烯酸乙酯。PMMA可被官能化,也即是说它可含有如酸、酰氯、醇、酸酐或脲基官能团。这些官能团可通过接枝或共聚引入。对于酸官能团,有利的是由丙烯酸或甲基丙烯酸共聚单体提供。两个相邻的丙烯酸官能团可通过脱水形成酸酐。
包括任选的官能团,官能团的比例可以是PMMA的0-15重量%。
PMMA可含有丙烯酸(酯)类弹性体。实际上商业可得PMMA的等级被称为“冲击等级”,它含有丙烯酸类冲击改性剂,其通常为核/壳类型。这些丙烯酸类冲击改性剂也可存在于PMMA中,因为它们可在聚合期间引入或在聚合同时制备。以重量计,相应于每100-70份PMMA,丙烯酸(酯)类弹性体的比例为0-30份。
对于丙烯酸(酯)类弹性体,它是指基于至少一种选自丙烯腈、(甲基)丙烯酸烷基酯的单体和核/壳共聚物的弹性体。对于核/壳共聚物,其形态为具有弹性体核和至少一个热塑壳的微粒,粒度一般小于1μm,并有利地为50-300nm。对于核的例子,可提及的是异戊二烯均聚物或丁二烯均聚物,异戊二烯与至多30mol%的乙烯基单体形成的共聚物和丁二烯与至多30mol%的乙烯基单体形成的共聚物。乙烯基单体可以是苯乙烯,烷基苯乙烯,丙烯腈或(甲基)丙烯酸烷基酯。其它核族包括(甲基)丙烯酸烷基酯的均聚物,以及(甲基)丙烯酸烷基酯与至多30mol%的选自另一种(甲基)丙烯酸烷基酯和乙烯基单体的单体形成的共聚物。有利的是,(甲基)丙烯酸烷基酯是丙烯酸丁酯。乙烯基单体可以是苯乙烯,烷基苯乙烯,丙烯腈,丁二烯和异戊二烯。核/壳共聚物的核可以全部或部分交联。所需要的是在制备该核期间加入至少为双官能的单体;这些单体可选自聚(甲基)丙烯酸的多元醇酯,比如二(甲基)丙烯酸丁二酯和三甲基丙烯酸三羟甲基丙烷酯。其它双官能单体例如二乙烯基苯,三乙烯基苯,丙烯酸乙烯酯和甲基丙烯酸乙烯酯。还可通过接枝和作为聚合中的单体将不饱和官能单体如不饱和羧酸酐、不饱和羧酸和不饱和环氧化物引入核,使核交联。例如,可提及的实例是马来酸酐,(甲基)丙烯酸和甲基丙烯酸缩水甘油酯。
壳是苯乙烯均聚物,烷基苯乙烯均聚物或甲基丙烯酸甲酯均聚物,或含有至少70mol%上述单体中的一种和至少一种选自其它的上述单体、其它的(甲基)丙烯酸烷基酯、乙酸乙烯酯和丙烯腈的共聚单体的共聚物。通过接枝和作为聚合中的共聚单体将不饱和官能单体如不饱和羧酸酐、不饱和羧酸和不饱和环氧化物引入壳将其官能化。例如,可提及的实例是马来酸酐,(甲基)丙烯酸和甲基丙烯酸缩水甘油酯。
例如,可提及的实例是具有聚苯乙烯壳的核/壳共聚物和具有PMMA壳的核-壳共聚物。也存在具有两个壳的核-壳共聚物,一个壳由聚苯乙烯制成,并且在外侧的另一个壳由PMMA制成。共聚物的例子以及它们的制备方法描述于下述专利中:US 4,180,494,US 3,808,180,US 4,096,202,US 4,260,693,US 3,287,443,US3 ,657,391,US 4,299,928,US 3,985,704和US 5,773,520。
有利的是,以重量计,核占核/壳共聚物的70-90%且壳占30-10%。
对于共聚物的例子,可提及的是共聚物的组成为75-80份的核(i),其含有至少93mol%丁二烯,5mol%苯乙烯和0.5-1mol%二乙烯基苯,以及25-20份的基本上等重的两个壳(ii),内壳由聚乙烯制成并且外壳由PMMA制成。
可提及的其它例子是具有聚(丙烯酸丁酯)或丙烯酸丁酯/丁二烯共聚物核和PMMA壳的核-壳共聚物。
对于导电填料(C),它可选自所有导电材料的粉末,并有利地为粉末金属,炭黑,石墨和金属氧化物。有利的是,(C)选自炭黑(优选pH为2-7)和石墨。有利的是,石墨(天然的或合成的)是薄片状形式。优选,其粒度在5-50μm之间。
本发明复合材料的制备是将各组分(A)、(B)和(C)溶于溶剂中,直至得到浓分散体为止,然后可将该分散体作为涂料涂布于基材上。所述溶剂可选自丙酮,异佛尔酮,二甲基甲酰胺(DMF),甲乙酮(MEK),N,N-二甲基乙酰胺和N-甲基吡咯烷酮(NMP)。本领域普通技术人员可根据PVDF的本性选择溶剂,即是取决于存在较多或较少量的均聚物。每份组合物所需溶剂的量可以是2-5份,以重量计。
基材可以是导电的,并在此情况下,其用作电流输入(current lead-in),并且导电材料放置于涂料上,该材料全部或部分覆盖涂料,从而允许电流返回。
有利的是,基材是电绝缘的;本发明组合物沉积于该基材上,并随后加入至少一个电流输入装置和至少一个电流返回装置。在涂布涂料之前这些装置就可已经存在。这些装置可以是铜线或铝线或铜条或铝条,这些线或条可以以电子工业中使用的印制电路方式在基材表面占相当大的部分。对于此种情况,该基材是绝缘板,其上有呈印制电路形式的两个-电流输入和返回-电极,并随后PTC组合物沉积于电路上,侧面带有电极。通过在覆盖有铜的印制电路的PET支持物上沉积20-30μm厚的PTC涂膜,可在13V的电压下加热到65℃,从而尤其可除去汽车后视镜的冰。
对于另一实施方案,绝缘基材是覆盖有本发明组合物的蜂窝器(honeycomb),例如将其浸入含有所述组合物(涂料)的溶剂中并随后蒸发溶剂。该蜂窝器可以是片状,块状,立方形或平行六面体形。选出两正对的面,并且在每个面上连接导体,其与覆盖蜂窝器的涂料接触。还可以用银漆(sliver lacquer)覆盖每个面代替固定导体。这些导体或银漆用于电流输入和返回。本发明还涉及这些蜂窝器用于加热气体如空气的用途。从而可加热机动车辆的乘客车厢或飞机的机舱。
对于另一实施方案,该基材可以是玻璃织物(woven glass fabric)(玻璃纤维网)。通过任何方式沉积涂料并随后增设电流输入和返回线,除非它们已存在于玻璃织物中。可使用任何绝缘体代替由玻璃制得的织物(wovenfabric)。浸渍了PTC涂料的网可用于下述应用:工业地板的除冰,船甲板的除冰,管道的加热,飞机行李舱(baggage hold)的加热等。
对于另一实施方案,该绝缘基材是软管(hose)的外层,该外层可由橡胶或热塑塑料(如聚酰胺,聚烯烃等)制成。电流输入和返回线可在涂布之后沉积,但优选它们沉积于软管的外层上。有利的是,它们是含有电流输入和返回线的编织物(braid)(例如由聚酯或聚酰胺制成)形式。随后沉积涂料并且有利的是,随后用保护层覆盖。该保护层可由热塑塑料(条件是它能经受住温度)或橡胶制成。从而,本发明是一种软管,其从里到外含有:
-任选地,与传输的液体相接触的内层;
-外层;
-根据本发明的涂料层和电流输入和返回装置;以及
-任选地,保护层。
涂料层可任选地涂于例如由聚酰胺或聚酯制成的编织或非编织基材上。
软管的内径可以是任意大小,并有利的是6-50mm。上述软管的厚度,也即是说任选的内层和外层的厚度总和可以为1-20mm。这些软管能输送任何类型的流体,但它们有助于输送在低温下结晶或形成阻塞物的流体。例如,可提及的是用于具有柴油机的机动车辆或货车的柴油机燃料,它通常含有蜡,而蜡在冬天或寒冷的国家会沉积而引起阻塞。
本发明还涉及含有上述复合材料的加热器。
附图说明
图1是从PVDF/PMMA/PVDF共聚物与石墨SFG15所制成的膜电阻率与温度的关系图,50微米厚,电极间2厘米。
图2是具有热半阻(thermal semi-block)下,对PVDF/PMMA/PVDF共聚物与32%石墨SFG15的组合物,功率和温度测量。
图3中,图3.1是从PVDF/PMMA/PVDF共聚物与填料所制成的膜电阻率与温度的关系图,电极间2厘米,厚度50微米;图3.2是具有热半阻时,在涂有PVDF/PMMA/PVDF共聚物(40%/30%/30%)和20%石墨SFG15的后视镜支持物上,功率和温度循环测量,1小时开/1小时关。
图4为在具有热半阻下,后视镜支持物上,对PVDF/MA接枝的PVDF/PMMA/PVDF共聚物与20%石墨SFG15,其功率和温度测量。
图5中,图5.1为在不具有热半阻下,蜂窝型支持物上,对PVDF/PMMA/PVDF共聚物与32%石墨SFG15,其功率和温度循环测量,30分钟开/20分钟关;图5.2为蜂窝器的照片。
具体实施方式
PVDF共聚物:是指Kynar9301,VF2/TFE/HFP共聚物,其各自的比例为72/18/10。
PVDF均聚物:是指Kynar500,PVDF均聚物,其MFI为4g/10min(在230℃/5kg)。
石墨SFG15:是指TIMREX SFG15型石墨,由Timcal集团生产。它是呈片状的合成石墨,且其粒度分布为0-20μm。
PMMA:是指含有MMA和丙烯酸乙酯的PMMA共聚物,其Tg为60℃且摩尔质量为140000。
炭黑:为RAVEN14型,由Columbian Chemicals Europa Gmbh(德国)生产。它为酸性pH。
马来酸酐接枝的PVDF:是指Kynar720,它是购自Atofina的PVDF均聚物且MVI(熔体体积指数(melt volume index))为10cm3/10min(230℃/5kg),其辐射接枝了1%的马来酸酐。
实施例1 PVDF/PVDF共聚物/PMMA/石墨
将20、25或30g石墨SFG15加入100gPVDF均聚物/PVDF共聚物/PMMA组合物中,该组合物各组分重量比例为40/30/30。在70℃及2000rpm下混合上述聚合物,以使NMP完全溶解。随后以3000rpm分散上述填料30分钟。
将该涂料涂于Teflon板(杜邦生产的聚四氟乙烯固体)上,随后在烘箱中于120℃下干燥,并于200℃下固化。从Teflon板上剥离得到膜并随后分析该膜。结果列于图1。填料含量越高,PTC效应的幅度(amplitude)就越小且起始电阻率就越低。由此可根据应用所需的功率调节成分配比。
实施例2 PVDF/PVDF共聚物/PMMA/石墨;涂于网上
将32g石墨SFG15加入100gPVDF均聚物/PVDF共聚物/PMMA组合物中,该组合物各组分重量比例为40/30/30。按照实施例1所示的相同方法制备涂料。
随后将该涂料涂于配有电极(网上每隔5cm设有铜线)的玻璃纤维网上,随后将其在120℃下干燥并在200℃下固化。通过使用设置于被该涂料浸渍过的网上的热半阻装置(聚合物基体,玻璃棉等),即玻璃棉或等价保护装置来改变稳定温度。结果列于图2。
实施例3 PVDF/PVDF共聚物/PMMA/石墨或炭黑;涂于覆盖有铜印
制电路的支持物上
将20g石墨SFG15或18g炭黑加入100gPVDF均聚物/PVDF共聚物/PMMA组合物中,该组合物各组分重量比例为40/30/30。按照实施例1所示的相同方法制备涂料。
在覆盖有铜印制电路的PET支持物上沉积20-30μm厚的PTC涂料膜,使其在13V电压在能加热到65℃,从而尤其可除去汽车后视镜的冰。涂上该涂料后,要在烘箱中于120℃下干燥。测量于13伏供电循环模式下的功率和温度(图3-2)。
还可按照实施例1,将该涂料在Teflon板上沉积形成50μm膜并且测定电阻率(图3-1)。结果,含炭黑的膜的PTC效应幅度大于含石墨的膜。但是,石墨能提供较好的热分散。
实施例4 PVDF/PVDF共聚物/PMMA/石墨-涂于覆盖者铝印制电路
的支持物上
由于PVDF内在的非粘合性,该涂料很难对铜印制电路尤其是铝印制电路具有好的粘合力。添加马来酸酐接枝的PVDF能使得材料具有好的粘合性并维持介电特性。
将20g石墨SFG15加入100g“PVDF均聚物”/PVDF共聚物/PMMA组合物中,该组合物各组分重量比例为40/30/30。40gPVDF均聚物是由20gPVDF均聚物和20g马来酸酐接枝的PVDF组成。按照实施例1所示的相同方法制备涂料。将该涂料沉积于后视镜支持物上,该支持物由覆盖有铝印制电路的PET板构成。结果列于图4。
当涂有PTC涂料的样品未使用时,可通过电阻计简单测定该样品的电阻(称为R计算)。当该后视镜处于电压下时,也可以通过计算测定该同样的电阻(称为R测量)。使用公式R=U/I。
“a”代表R测量与R计算的比值。
样品1 | 样品2 | |||||
测试号 | R<sub>测量</sub> | R<sub>计算</sub> | a1 | R<sub>测量</sub> | R<sub>计算</sub> | a2 |
1 | 14.8 | 13.4 | 1.10 | 10.1 | 10.2 | 0.99 |
2 | 13.8 | 12.9 | 1.07 | 10.1 | 10.3 | 0.98 |
3 | 14.2 | 12.4 | 1.15 | 10.3 | 10.4 | 0.99 |
4 | 13.4 | 12.9 | 1.04 | 10.2 | 10.1 | 1.01 |
(其中样品1=本实施例组合物,但PVDF均聚物是完全的非接枝PVDF均聚物;样品2=本实施例组合物)。
由此可见,含有马来酸酐接枝的PVDF的PTC涂料能更好的与铝印制电路电接触。此外,电阻更恒定,且在施加电压后更迅速地回复到稳定电阻值。
实施例5 PVDF/PVDF共聚物/PMMA/石墨-涂于蜂窝型三维支持物
上
将涂料涂于三维支持物上使得热转移交换的表面积显著增加。
将32g石墨SFG15加入100gPVDF均聚物/PVDF共聚物/PMMA组合物中,该组合物各组分重量比例为40/30/30。按照实施例1所示的相同方法制备涂料。
一旦蜂窝器涂上该涂料后,就要在烘箱中于120℃及随后180℃下干燥。随后将一层薄银漆沉积于样品的每个侧面以确保电连接。沉积于样品每一侧的两个金属栅格(grid)还可用作电接点。结果列于图5-1。图5-2中所示照片为该蜂窝器。
Claims (23)
1.一种组合物,以总重量100%计,包含:
A)40-80%的聚偏1,1-二氟乙烯;
B)10-40%的聚甲基丙烯酸甲酯;和
C)10-40%的导电填料。
2.根据权利要求1的组合物,其中聚偏1,1-二氟乙烯选自1,1-二氟乙烯/四氟乙烯/六氟丙烯共聚物,其各摩尔组成为60-80/15-20/0-25,总和为100。
3.根据权利要求1的组合物,其中聚偏1,1-二氟乙烯选自含有至少60重量%1,1-二氟乙烯的1,1-二氟乙烯共聚物,共聚单体选自氯三氟乙烯、六氟丙烯、三氟乙烯和四氟乙烯。
4.根据权利要求1的组合物,其中聚偏1,1-二氟乙烯A是A1和A2的共混物,A1选自聚偏1,1-二氟乙烯均聚物和含有至少85重量%1,1-二氟乙烯的1,1-二氟乙烯/六氟丙烯共聚物,A2是各摩尔组成为60-80/15-20/0-25的1,1-二氟乙烯/四氟乙烯/六氟丙烯共聚物,总和为100。
5.根据权利要求4的组合物,其中A1和A2的比例A1/A2以重量计为20/80-80/20。
6.根据前述任一项权利要求的组合物,其中聚偏1,1-二氟乙烯被全部或部分改性,并且其选自:
接枝了不饱和单体的聚偏1,1-二氟乙烯,在无氧下,通过辐射共混物进行接枝;
在有氧下辐射的聚偏1,1-二氟乙烯;和
脱氟化氢并随后氧化的聚偏1,1-二氟乙烯。
7.根据权利要求6的组合物,其中改性聚偏1,1-二氟乙烯占A的0.5-30%重量。
8.根据权利要求6的组合物,其中聚偏1,1-二氟乙烯A1被全部或部分改性。
9.根据权利要求7的组合物,其中聚偏1,1-二氟乙烯A1被全部或部分改性。
10.根据前述权利要求1-5任一项所述的组合物,其中填料C选自石墨和炭黑。
11.根据权利要求6所述的组合物,其中填料C选自石墨和炭黑。
12.根据权利要求7所述的组合物,其中填料C选自石墨和炭黑。
13.根据权利要求8所述的组合物,其中填料C选自石墨和炭黑。
14.根据权利要求9所述的组合物,其中填料C选自石墨和炭黑。
15.PTC涂料,含有1份根据权利要求1-14中任一项的组合物和2-5份溶剂,其中溶剂选自丙酮,异佛尔酮,二甲基甲酰胺,甲乙酮,N,N-二甲基乙酰胺和N-甲基吡咯烷酮。
16.一种复合材料,其含有全部或部分涂有根据前述权利要求1-14中任一项所述组合物的基材。
17.根据权利要求16的复合材料,其中该基材是由绝缘体形成的蜂窝器。
18.根据权利要求17的复合材料,其中在蜂窝器两正对面的每个面上有充当电流输入和电流返回的导体。
19.权利要求17或18的复合材料用于加热气体的用途。
20.根据权利要求19的用途,其中所述用途为加热机动车辆的乘客车厢或飞机的机舱。
21.根据权利要求16的复合材料,其中该基材是玻璃或绝缘体的织物。
22.加热器,含有根据权利要求16,17,18和21任一项所述的复合材料。
23.一种软管复合材料,其从里到外含有:
-任选的,与传输的流体相接触的内层;
-外层;
-根据权利要求1-14任一项所述的组合物层和电流输入和电流返回手段;以及
-任选的,保护层。
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FR0402395 | 2004-03-08 |
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CN100365080C true CN100365080C (zh) | 2008-01-30 |
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NO (1) | NO20043232L (zh) |
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JP6179850B2 (ja) * | 2013-03-19 | 2017-08-16 | Littelfuseジャパン合同会社 | Ptc組成物 |
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WO2018212064A1 (ja) * | 2017-05-19 | 2018-11-22 | 株式会社カネカ | 溶剤組成物およびその製造方法 |
KR20210096625A (ko) * | 2018-11-26 | 2021-08-05 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | Vdf 중합체 및 흑연을 포함하는 중합체 조성물 |
JP6831896B1 (ja) * | 2019-11-27 | 2021-02-17 | 関西ペイント株式会社 | 導電性顔料ペースト、塗工材、及び導電性塗工膜 |
CN111096705A (zh) * | 2019-12-29 | 2020-05-05 | 苏州路之遥科技股份有限公司 | 一种可拆卸式加热马桶圈的生产工艺 |
JP6850936B1 (ja) * | 2020-12-24 | 2021-03-31 | 関西ペイント株式会社 | 導電性顔料ペースト、塗工材、及び導電性塗工膜 |
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JP2005054185A (ja) | 2005-03-03 |
NO20043232L (no) | 2005-02-02 |
CN1616564A (zh) | 2005-05-18 |
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