CN101605845A - 填充有炭黑并且具有高介电常数和击穿强度的聚氨酯 - Google Patents

填充有炭黑并且具有高介电常数和击穿强度的聚氨酯 Download PDF

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CN101605845A
CN101605845A CNA2008800042191A CN200880004219A CN101605845A CN 101605845 A CN101605845 A CN 101605845A CN A2008800042191 A CNA2008800042191 A CN A2008800042191A CN 200880004219 A CN200880004219 A CN 200880004219A CN 101605845 A CN101605845 A CN 101605845A
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W·詹宁杰
B·科勒
J·瓦格纳
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Abstract

本发明涉及填充有炭黑的聚氨酯,其特征在于具有高介电常数和击穿强度,并且由通过DMC催化制得的聚环氧烷组成。

Description

填充有炭黑并且具有高介电常数和击穿强度的聚氨酯
本发明涉及填充有炭黑的、优选柔性的、聚氨酯,其特征在于具有高介电常数和击穿强度,并且由聚环氧烷合成得到。
本发明的目的在于提供具有高介电常数和高击穿电压的聚氨酯复合物(Polyurethan-Compound),其对于例如在电容器中用作介电材料(Dielektrikum)是有吸引力的。
填充有炭黑的具有高模量的导电聚氨酯由Novak在EuropeanPolymer Journal(2004)40(7),1417-1422中进行了描述。然而,导电化合物被作为介电材料的应用所排除。
由炭黑和含水聚氨酯分散体制造的复合物在多种参考文献书目中得到了描述:Material Letters(2004)58(27-28),3606-3609;ChineseChemical Letters(2004)15(8),1001-1004;Sensors and Actuators,B:Chemical(2005)B105(2),187-193。
具有0.7%的低炭黑含量的已知聚氨酯混合物已经显示出渗滤作用,其中导电率在直至超过10%的炭黑含量的宽范围内升高,并且受气体和溶剂蒸汽作用的显著影响。这种行为意味着它们适于用作气体传感器,但是不适宜用作介电材料。
Altafim在Materials Research(2003)6(2),187-191中描述了填充有炭黑的聚氨酯,其中含有蓖麻油作为多元醇组分。然而,这种复合物具有过高的模量,因为蓖麻油的OH当量为350g/当量。
US 2006096694-A描述了具有高介电常数的非传导性粘合剂,但是,其具有由所含聚酯多元醇导致的高模量。然而,具有低模量的复合物对于一些特定应用是期望的。
现在发现了特征在于高介电常数和击穿电压的填充有炭黑的聚氨酯,其含有由DMC(双金属氰化物)催化制得的聚醚作为结构单元。在给定的介电常数条件下,含有由碱金属氢氧化物催化制得的聚环氧烷或者含有聚-THF的聚氨酯的可比较复合物不能达到所述新复合物的击穿强度。
本发明提供填充有炭黑的聚氨酯物料,至少由以下组分组成
A)99.9-70重量%的聚醚尿烷,其中结合有(eingebaut)多元醇组分,该聚醚尿烷由以下组成
a)50-100重量%的由DMC催化制得的聚环氧烷,特别是环氧丙烷,和
b)0-50重量%的无催化剂残余的多元醇,特别是已经通过蒸馏或者重结晶纯化的那些多元醇,或者不是由含氧的杂环族化合物(Sauerstoffheterocyclen)的开环聚合制得的那些,
B)0.1-30重量%的炭黑。
在该新颖的聚氨酯中使用的多元醇组分a)的实例是描述在WO97/29146、EP-A 700 949和EP-A 761 708中的那些多元醇。它们是可以通过环氧化物的开环聚合获得的聚环氧烷,其中在开环聚合中使用85-100%,优选100%的环氧丙烷,和剩余物可以由环氧丁烷、环氧己烷、乙烯基环氧乙烷(Vinyloxiran)、烯丙基缩水甘油醚、丁基缩水甘油醚、乙基己基缩水甘油醚、表氯醇、环氧乙烷、苯基缩水甘油醚或者甲酚基缩水甘油醚(Kresylglycidylether)组成。双金属氰化物(DMC)配合物,例如六氰钴酸锌,被用作催化剂。所述聚环氧烷在聚氨酯中的有利应用已经描述在US 6825376和US 2004067315中,然而,对于力争取得的应用,所述多元醇在与异氰酸酯的反应中的更高选择性是惊人的。
结合到根据本发明使用的聚氨酯混合物中的多元醇组分a)的摩尔质量(数均分子量Mn)优选为1000-14000g/摩尔,特别优选1500-8500g/摩尔。其官能度优选为2-6,特别优选2。
作为多元醇组分b),优选使用乙二醇、二乙二醇、三甘醇、四甘醇、丙二醇、二丙二醇、三丙二醇、四丙二醇、TMP、新戊二醇、季戊四醇、环己烷二甲醇、丁二醇、蓖麻油、脱水蓖麻油、氢化蓖麻油、二聚体二醇(Dimerdiol)、己二醇、癸二醇、十二烷二醇、羟基官能化的低聚丁二烯、氢化的羟基官能化的低聚丁二烯、甘油或者TMP单烯丙基醚。
优选聚氨酯A)通过以下方式制得:使多元醇组分a)和任选的b)与1.0-1.1当量的多异氰酸酯在15-120℃的温度下,优选18-80℃,在NCO-OH反应的催化剂(比如锡化合物或者胺)存在或者不存在下进行反应。组分a)、任选的b)、多异氰酸酯和B)的混合尤其是在可以给予高剪切能量的适宜混合器中进行,比如,例如在Speed-Mixer中进行,和如果必要,通过另外的超声作用进行。
作为多异氰酸酯,优选使用选自以下的那些:HDI,三甲基-HDI,IPDI,十二氢-MDI,降冰片烷二异氰酸酯,双异氰酸根合甲基环己烷,双异氰酸根合甲基苯,TMXDI,2,4-TDI或者2,6-TDI或者它们的混合物,2,2-MDI、2,4-MDI或者4,4-MDI或者它们的混合物,含3-核或者含寡聚-MDI的MDI类型,其中优选脂族异氰酸酯,碳二亚胺或者上述二异氰酸酯的含有4-环或者6-环杂环的二聚体或三聚体,它们与比如TMP、二乙二醇或者二丙二醇的低分子量多元醇的加合物,和它们在多元醇上的尿烷或者脲基甲酸酯预聚物,这对应于上述组分a)。特别优选脲基甲酸酯预聚物,比如描述在US 2005222365中的那些,其中在优选的实施方案中,对应于以上所述的组分a)的聚环氧烷被用作多元醇。特别是可以有利地使用摩尔质量在Mn=2000~HDI范围的通过DMC催化制得的聚环氧丙烷的脲基甲酸酯预聚物,其中脲基甲酸酯化反应优选用辛酸锌催化,和聚环氧丙烷的脲基甲酸酯预聚物对应于式I:
式(I),
其中n是30~38的数字。
组分B)的炭黑是特别细碎分散的炭黑类型,比如可以由例如Degussa AG商业获得。通常使用平均粒度至多1μm的炭黑类型,优选至多100nm和特别优选至多50nm。应当同时优选炭黑具有大BET表面积,特别是BET表面积大于250m2/g,优选大于500m2/g和特别优选大于900m2/g。
根据本发明的炭黑填充的聚氨酯可以在用于将机械能转化为电能和将电能转化为机械能的设备中用作介电材料。这样的能量转化器在例如US-A-6343129中进行了描述。
实施例1(对比实施例)
所有液体原料都在氩气下以三阶段法小心地脱气,和将炭黑经125μm的筛过筛。称取10g Terathane 650(INVISTA GmbH,D-65795Hatterheim,摩尔质量Mn=650的聚-THF)与0.596g炭黑(KetjenblackEC 300J,由Akzo Nobel AG生产),置入60ml的单向混合容器(APM-Technika AG,订单号.1033152)中,和在Speedmixer(得自于APM-Technika AG,CH-9435 Heerbrugg;销售D:Hauschild;型号DAC150FVZ)中,在3000转每分下混合3分钟,从而形成均匀的浆料。然后,称重取出0.005g二月桂酸二丁锡(Metacure
Figure G2008800042191D00041
T-12,Air Productsand Chemicals,Inc.)和6.06g异氰酸酯N3300(产品得自于BayermaterialScience AG),置入浆料中,并且在Speedmixer中,在3000转每分下混合1分钟。将反应浆料倾倒在玻璃板上和用刮刀涂布至湿层厚度为500μm,从而形成固体含量为2%的均匀薄膜。然后,在80℃下将该薄膜加热16小时。
热处理后的薄膜性能在下表1中给出。
实施例2(根据本发明)
所有液体原料都在氩气下以三阶段法小心地脱气,和将炭黑通过125μm的筛过筛。称取10g Arcol PPG 2000(产品得自于BMS AG,平均摩尔质量Mn=2000的DMC-催化的聚环氧丙烷)与0.636g炭黑(Ketjenblack EC 300型号),置入60ml单向混合容器中,和在Speedmixer中,在3000转每分下混合三分钟。然后,称取0.005g二月桂酸二丁锡和7.13g异氰酸酯Desmodur XP 2599(产品得自于BayerMaterialScience AG,式I的脲基甲酸酯预聚物,其中Arcol PPG 2000被用作聚环氧烷),置入浆料中,和在Speedmixer中,在3000转每分下混合1分钟。将反应浆料倾倒在玻璃板上和用刮刀涂布至湿层厚度为500μm,从而形成固体含量为2%的均匀薄膜。然后,在80℃下将该薄膜加热16小时。
热处理后的薄膜形成在下表1中给出。
表1:测量数据
  实施例   固体含量%   DC介电常数   DC单位体积导电率S/cm   击穿电场强度MV/m
  1   2   <4   5E-6   5
  2   2   700   6E-11   30
根据本发明的聚氨酯物料的优点在于显著更高的介电常数和显著降低的单位体积导电率以及显著更高的击穿电场强度。

Claims (9)

1.填充有炭黑的聚氨酯物料,至少由以下组成
A)99.1-70重量%的聚醚尿烷,其中结合有多元醇组分,该聚醚尿烷由以下组成
a)50-100重量%的通过DMC催化制得的聚环氧烷,特别是聚环氧丙烷,和
b)0-50重量%的无催化剂残余的多元醇,特别是已经通过蒸馏或者重结晶纯化的那些多元醇,或者是并非由含氧的杂环族化合物的开环聚合制得的那些多元醇,
B)0.1-30重量%的炭黑。
2.根据权利要求1的聚氨酯,其特征在于多元醇组分a)为100重量%。
3.根据权利要求1或者2的聚氨酯,其特征在于脲基甲酸酯预聚物被用作异氰酸酯。
4.根据权利要求1~3至少一项的聚氨酯,其特征在于,使用脲基甲酸酯预聚物作为异氰酸酯,其含有通过DMC催化制得的聚环氧烷作为多元醇组分。
5.根据权利要求1~4至少一项的聚氨酯,其特征在于,使用根据式(I)的脲基甲酸酯预聚物作为异氰酸酯
Figure A2008800042190003C1
式(I)n=30-38
和/或聚氨酯基于这样的预聚物,其中该预聚物基于的聚环氧丙烷通过DMC催化制得。
6.根据权利要求1~5至少一项的聚氨酯在用于将机械能转化为电能和将电能转化为机械能的能量转换器中作为介电材料的用途。
7.含有根据权利要求1~6之一的聚氨酯物料的薄膜或者涂料。
8.含有根据权利要求1~5之一的聚氨酯物料作为介电材料的能量转换器。
9.含有根据权利要求1~5之一的聚氨酯物料作为介电材料的电容器。
CN2008800042191A 2007-02-07 2008-01-26 填充有炭黑并且具有高介电常数和击穿强度的聚氨酯 Expired - Fee Related CN101605845B (zh)

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US20080188615A1 (en) 2008-08-07
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