CN106977917B - 用于碱性电池的聚酰胺填充密封物 - Google Patents
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- 229920002647 polyamide Polymers 0.000 title claims abstract description 19
- 239000004952 Polyamide Substances 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000000945 filler Substances 0.000 claims abstract description 14
- 229920000305 Nylon 6,10 Polymers 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 11
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 37
- 238000000465 moulding Methods 0.000 claims description 7
- 239000004609 Impact Modifier Substances 0.000 claims description 5
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- 239000003063 flame retardant Substances 0.000 claims description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- 239000011487 hemp Substances 0.000 description 1
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- 230000007794 irritation Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical group NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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Abstract
本发明涉及用于碱性电池的填充密封物,其由聚酰胺组合物制成,该聚酰胺组合物包括至少有聚酰胺66和聚酰胺610以及任选填料和/或添加剂。所述填充密封物特别适合标准的“AAA”(LR03)和“AA”(LR6)电池。
Description
本申请是申请号为201180019029.9、申请日为2011年4月12日、名称为“用于碱性电池的聚酰胺填充密封物”的专利申请的分案申请。
本发明涉及用于碱性电池的填充密封物,其由聚酰胺组合物制成,所述聚酰胺组合物包含至少有聚酰胺66和聚酰胺610;以及任选填料和/或添加剂。这些填充密封物特别适合用于碱性电池,如标准的“AAA”(LR03)和“AA”(LR6)棒电池。
碱性电池是这样类型的电池,其通过锌(Zn)与二氧化锰(MnO2)之间的氧化还原而工作,其名称取自这样的事实,即其被命名为正极和负极的两个电极是浸在氢氧化钾(KOH)碱性电解质中的。
碱性电池可制成圆柱和钮扣的形式。圆柱形电池容纳在充当阴极电流收集器的钢管中。这种电池包含以碳粉补充(以提高导电性)的压缩二氧化锰膏剂的混合物。可将这种膏剂灌入管中或者以预成形环的形式插入。阴极的中心孔涂以隔离物,所述隔离物防止阳极产物与阴极产物混合并防止电池元件短路。阳极由在含有氢氧化钾电解质的凝胶中的锌粉分散体构成。在标准的棒型电池中,阳极对应于扁平端,而阴极是带有突出头的那端。
随着时间的推移,碱性电池容易发生氢氧化钾的泄漏,氢氧化钾是腐蚀性物质,其引起呼吸道、眼部和皮肤刺激,并导致电池的性能随时间的推移而降低。因此就有了填充密封物,也称垫片,其使得能够减缓或防止氢氧化钾的泄漏。这些填充密封物可基于聚酰胺66,如专利申请US 2006/0 222 938中所提到的。这些填充密封物也可由聚酰胺612或聚酰胺610构成,如专利申请WO 2009/087 798中所提到的。然而,这些聚酰胺树脂表现得不能充分保留氢氧化钾并且不耐氢氧化钾。
本申请人已经完全出人意料地发现,由聚酰胺66和聚酰胺610的混合物有可能产生用于碱性电池的填充密封物,这种填充密封物具有完全令人满意的性能,并且特别地具有对氢氧化钾的化学耐性,能够实现泄漏的大幅度减少,这与在本领域中常规使用的其它聚酰胺基质相比要有效得多。
因此本发明的主旨为用于碱性电池的填充密封物,其由聚酰胺组合物制成,所述聚酰胺组合物包含至少有聚酰胺66和聚酰胺610;以及任选填料和/或添加剂。本发明还涉及这种组合物用于减少或防止氢氧化钾从碱性电池中泄漏的用途。
相对于组合物的总重量来说,组合物优选包含按重量计30%至70%的聚酰胺66和按重量计30%至70%的聚酰胺610。
聚酰胺66和610在文献中有很好的描述,特别是在M.I.Kohan的“尼龙塑料手册(Nylon Plastics Handbook)”(Hanser,1995)中有很好的描述。术语“聚酰胺66”特别是指包含按质量计至少80%的六亚甲基己二酰胺单元的聚酰胺。术语“聚酰胺610”特别是指包含按质量计至少80%的六亚甲基癸二酰胺单元的聚酰胺。这些聚酰胺可因此完全为(共)聚酰胺。通常热共混聚酰胺66和610,特别是通过挤出而热共混的。
根据本发明的组合物还可以包含常规用于生产聚酰胺组合物的添加剂。因此,可以提到的有润滑剂、阻燃剂、增塑剂、成核剂、冲击改性剂、增强填料或增量填料、催化剂、光和/或热稳定剂、抗氧化剂、抗静电剂、着色剂、控油剂、模制助剂或其它常规的添加剂。
根据本发明的增强填料或增量填料可以是例如纤维性填料和/或非纤维性填料。
可以提到的纤维性填料包括玻璃纤维、碳纤维、天然纤维、芳纶纤维和纳米管,特别是碳纳米管。作为天然纤维,可以提到的有大麻和亚麻。非纤维性填料当中,特别可以提到任何颗粒或层状填料和/或可脱落或不可脱落的纳米填料,例如氧化铝、炭黑、铝硅酸盐粘土、蒙脱土、磷酸锆、高岭土、碳酸钙、硅藻土、石墨、云母、二氧化硅、二氧化钛、沸石、滑石、钙硅石、聚合物填料(例如二甲基丙烯酸酯颗粒)、玻璃珠或玻璃粉。
根据本发明,组合物完全有可能包含若干类型的增强填料。优选地,最常用的填料可以是切碎类型的玻璃纤维,特别是直径在7μm与14μm之间的玻璃纤维。这些填料可具有能确保纤维与聚酰胺基质之间机械粘附的表面胶料。
相对于组合物的总重量来说,增强填料或增量填料的重量浓度有利的是按重量计在1%与60%之间,优选按重量计在15%与50%之间。
特别是可以向聚酰胺组合物中添加抗冲击性调节剂。弹性体聚合物通常可用于此目的。弹性调节剂通常被定义为具有小于约500MPa的拉伸模量ASTM D-638。适合使用的弹性体的例子有乙烯-丙烯酸酯-马来酸酐、乙烯-丙烯-马来酸酐、任选具有接枝马来酸酐的乙烯-丙烯-二烯单体(EPDM)。
包含聚酰胺反应性官能团的冲击改性剂是特别优选的。可以提到的例子包括乙烯、丙烯酸酯和甲基丙烯酸缩水甘油酯的三元共聚物;乙烯和丙烯酸丁酯的共聚物;乙烯、丙烯酸正丁酯和甲基丙烯酸缩水甘油酯的共聚物;乙烯和马来酸酐的共聚物;接枝有马来酸酐的苯乙烯/马来酰亚胺共聚物;以马来酸酐改性的苯乙烯/乙烯/丁烯/苯乙烯共聚物;接枝有马来酸酐的苯乙烯/丙烯腈共聚物;接枝有马来酸酐的丙烯腈/丁二烯/苯乙烯共聚物;以及它们的氢化形式。这些剂在总组成中的重量比例特别地在0.1%与40%之间,优选在5%与20%之间。
特别优选的组合物是相对于组合物的总重量来说包含以下物质的组合物:
按重量计30%至70%的聚酰胺66;
按重量计30%至70%的聚酰胺610;
按重量计0.1%至40%的抗冲击性调节剂。
可以通过适合于每种填料或添加剂的惯用方式将这些填料和添加剂加入到聚酰胺组合物中,例如在聚合期间加入或者在熔体中混合。
本发明的组合物通常是通过以下的方式得到的:将各种成分进行热共混,例如在单螺杆或双螺杆挤出机中热共混,其温度足以将聚酰胺树脂保持在熔融介质中;或者通过冷共混,特别是在机械混合器中冷共混。一般情况下,将所得到的混合物以棒的形式挤出,所述棒被切碎成块以形成粒料。可以在塑料材料生产过程中的任何时刻加入所述化合物,特别是通过与塑料基质进行热共混或冷共混。可以通过以下方式进行化合物和添加剂的添加,将这些化合物以纯形式或在基质(例如塑料基质)中的浓缩混合物的形式加入到该熔融塑料基质中。
该组合物优选为模制组合物,例如形式为粒料或粉末,特别用来生产制品,尤其是通过模制或注入模制过程生产制品。根据本发明的组合物可用于任何形成塑料材料的过程,例如模制过程(特别是注入模制、转动模制)、烧结或浇注或挤出过程(如吹塑挤出和薄膜挤出)或者是纺丝过程。因此本发明还涉及通过形成本发明的组合物来生产模制或挤出制品的方法。
本发明的填充密封物可用于各种类型的碱性电池,特别是纽扣电池或圆柱形电池。棒型标准电池“AAA”(LR03)、“AA”(LR6)、“C”(LR14)、“Sub-C”和“D”是特别优选的。电池的格式由国际电工技术委员会(CEI)和由美国国家标准协会(ANSI)标准化。这些电池可以是可再充电的或不可再充电的。
本发明还涉及碱性电池,这种碱性电池包括发电元件和根据本发明的填充密封物。
本发明还涉及通过模制根据本发明的组合物来生产填充密封物的方法。
说明书中使用了特定的术语以便帮助理解本发明的原理。然而应该理解的是,使用这些特定的术语并不意味着限制本发明的范围。相关技术领域的技术人员根据其一般知识可以特别地设想出修改、改进和完善方案。术语“和/或”包括“和”、“或”以及与此术语相关联的元件的所有其它可能的组合的含义。根据下文仅通过指示方式给出的实施例可以更清楚地看出本发明的其它细节或优点。
实验部分
如下所述制备和测试实例1和2以及比较实例C1和C2的组合物:
所使用的化合物如下:
A-1:聚酰胺66Technyl 26A,由罗地亚(Rhodia)生产,相对粘度为2.6(在23℃用按重量计1%的硫酸测定),熔点为262℃
A-2:聚酰胺610,相对粘度为2.8(在23℃用按重量计1%的硫酸测定),熔点为218℃
B:接枝有马来酸酐的乙烯-丙烯弹性体,由韩国Keumho Petrochemical以商品名Kepa 1150销售
C:滑石(#600目)
D:包含抗氧化剂和润滑剂的添加剂
通过在双螺杆挤出机(内径30mm;L/D=30)中将这些化合物混合来生产组合物。挤出机的温度分布是在260℃与280℃之间。在50-70cmHg真空下的挤出速率在250rpm与300rpm之间。
将干燥后得到的颗粒在Engel注入压机中进行成形,压缩力为80吨,注入体积为189.44cc。料筒温度为280℃,模具温度为80℃。注入和冷却周期约15秒。根据要进行的测试制出各样本。还制出填充密封物并与LR6碱性电池进行组装,用于KOH泄漏测试。
测试配制品,结果在下表1中给出:
表1
nm=未测量
根据标准ASTM D-648测定HDT(18.5kgf/cm2)。
对于32个填充密封物在视觉上观察漂白作用。
将含有40%的KOH电解质的50LR6碱性电池在71℃下放置10周,在其上观察到KOH泄漏。在每个周末,在视觉上观察泄漏显著的电池的数目。
如此在表1中可看出,实施例1和2的配制品比现有技术配制品对KOH的化学耐性要好得多。
Claims (6)
1.一种用于碱性电池的填充密封物,该填充密封物由聚酰胺组合物制成,该聚酰胺组合物包含:相对于该组合物的总重量来说按重量计30%至70%的聚酰胺66和相对于该组合物的总重量来说按重量计30%至70%的聚酰胺610;抗冲击性调节剂;以及任选的填料和/或添加剂,其中该组合物中所有组分的总和等于100重量%。
2.根据权利要求1所述的填充密封物,其特征在于,该组合物包含选自下组的添加剂,该组由以下各项组成:润滑剂、阻燃剂、增塑剂、成核剂、增强填料或增量填料、催化剂、光和/或热稳定剂、抗氧化剂、抗静电剂、着色剂、控油剂和模制助剂。
3.根据权利要求1或2所述的填充密封物,其特征在于,相对于该组合物的总重量来说,该组合物包含:
按重量计30%至70%的聚酰胺66;
按重量计30%至70%的聚酰胺610;
按重量计0.1%至40%的抗冲击性调节剂。
4.一种碱性电池,包括发电元件和根据权利要求1至3中任一项所述的填充密封物。
5.一种方法,用于通过模制根据权利要求1至3中任一项所述的组合物来生产填充密封物。
6.根据权利要求1至3中任一项所述的组合物用于减少或防止氢氧化钾从碱性电池中泄漏的用途。
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