CN1536702A - 燃料电池中的液体和气体的管路*** - Google Patents
燃料电池中的液体和气体的管路*** Download PDFInfo
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- CN1536702A CN1536702A CNA2004100325298A CN200410032529A CN1536702A CN 1536702 A CN1536702 A CN 1536702A CN A2004100325298 A CNA2004100325298 A CN A2004100325298A CN 200410032529 A CN200410032529 A CN 200410032529A CN 1536702 A CN1536702 A CN 1536702A
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- Prior art keywords
- layer
- fuel cell
- polyolefin
- poly
- polyester
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- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D2/00—Hair-curling or hair-waving appliances ; Appliances for hair dressing treatment not otherwise provided for
- A45D2/02—Hair winders or hair curlers for use substantially perpendicular to the scalp, i.e. steep-curlers
- A45D2/10—Hair winders or hair curlers for use substantially perpendicular to the scalp, i.e. steep-curlers in the form of spools or bobbins
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D2/00—Hair-curling or hair-waving appliances ; Appliances for hair dressing treatment not otherwise provided for
- A45D2/12—Hair winders or hair curlers for use parallel to the scalp, i.e. flat-curlers
- A45D2/122—Means for fastening the hair on the curler body
- A45D2/125—Flexible fastening means
-
- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D2/00—Hair-curling or hair-waving appliances ; Appliances for hair dressing treatment not otherwise provided for
- A45D2/36—Hair curlers or hair winders with incorporated heating or drying means, e.g. electric, using chemical reaction
- A45D2/365—Hair curlers or hair winders with incorporated heating or drying means, e.g. electric, using chemical reaction with chemical heating means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
- B60L50/70—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by fuel cells
- B60L50/72—Constructional details of fuel cells specially adapted for electric vehicles
-
- H—ELECTRICITY
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Abstract
本发明涉及燃料电池的管路***的元件,其中与输送的介质接触的部件由聚酯成型材料组成,此外,至少存在另一层,其选自a).由聚酰胺成型材料组成的层II,b).由官能化的聚烯烃组成的成型材料制成的层III.c).由聚烯烃成型材料制成的层IV,其中该聚烯烃是未官能化的以及d).由EVOH-成型材料制成的层V。其可以低成本地制备,对输送的介质具有好的阻挡作用,以及基本上不释放使催化剂中毒或者极化的组分。
Description
技术领域
本申请的内容是一种燃料电池的管路***元件,该元件与液体和气体接触。
背景技术
越来越严格的环境立法正迫使机动车的制造商考虑新的推进***,因为恰好是NOx释放越来越成为立法者关注的焦点。燃料电池是一种可能的替代的推进***。
长期以来,现有技术中已知各种不同的燃料电池实施方式。这些燃料电池的共同点是将燃料加入阳极室,而将空气或氧加入阴极室中。在这些电极上这些反应剂进行催化反应。使用的燃料可以包括氢、甲醇、乙二醇、甲烷、丁烷、高级烃等,然而首先只有获得高的电流密度,才能将在接近室温下工作的燃料电池用于推进机动车。常规的燃料仅是在中温或高温燃料电池中能令人满意地反应,但是这主要适合于固定式设备。因此,在电气驱动的机动车(它们的电流从燃料电池组中获取,该燃料电池组应该是被甲醇或烃推动的)中,燃料通常在较高温下在转化器中通过水蒸气转化为氢和二氧化碳,反应气体中无副产物一氧化碳,并且将氢-CO2混合物输送到阳极室中。目前“质子交换膜燃料电池”对此是有利的,其中在多孔的含催化剂的电极之间是水饱和的酸性离子交换膜。然而,对于移动应用来说甲醇的直接氧化也是研究的课题,这使得转化器不是必要的。
直到现在,用于燃料输送的管路一般是由优质钢制备的。然而这种管路是昂贵的。
JP 200-213659A公开了一种用于氢的管路,其由聚烯烃内层、EVOH-中间层和聚酰胺外层组成。这里通过未详细说明的粘结剂的使用清楚地看出这些层之间通常存在缺少粘性的问题。
与此相比,本发明的任务是提供一种燃料电池的管路***的元件,其对烃、醇和氢具有改善的阻挡作用,此外在这种情况下单个层就本身而言是相互牢牢地粘结在一起的。
再者,应绝对确保尽可能地无组分从该管路体系的材料中溶出(这些组分可以与电解质或阳极材料反应),以便防止催化剂的中毒或者所不希望的极化。
在未公开的欧洲专利申请号02 018 541.9中描述了一种燃料电池的管路***的元件,其中与输送的介质相接触的部件由聚酯模制材料组成。由此,通过燃料电池的管路***的元件完成了上述任务,在该元件中
-与输送的介质接触的最内层I由聚酯模制材料组成,
-此外,至少存在另一层,其选自
a)由聚酰胺模制材料组成的层II,
b)由官能化的聚烯烃组成的模制材料制成的层III,
c)由聚烯烃模制材料制成的层IV,其中该聚烯烃是未官能化的,以及
d)由EVOH-模制材料制成的层V。
这种元件例如是管或管状模制部件,其可以是多层管,其中最内层由聚酯模制材料组成。这种管或管状模制部件或者作为随后如果需要可被热成型的平滑管或者作为波形管制备。此外,还可以提及一些在其中储存液体的构件,例如贮备容器。其它元件例如是连接件、一些所谓的快速连接器、转接器、过滤器、泵中的元件或阀中的元件。
发生内容
本发明的元件可以借助于常规的塑料加工方法来制备,例如借助于共挤压(例如多层管)、吹模或与其特殊形式例如吸入吹膜或3D软管操作(其中共挤出型坯)、注射成型和其特殊方法如液体注射技术、或旋转烧结。
本发明的元件例如从外向内可具有下列的层结构:
II/I
II/粘结剂/I
III/II/粘结剂/I
IV/III/II/粘结剂/I
IV/粘结剂/I
II/V/II/粘结剂/I
II/III/V/III/II/粘结剂/I
III/I
IV/III/I
IV/III/V/III/I
II/V/粘结剂/I
热塑性聚酯可以通过二元醇与二元羧酸或其形成聚酯的衍生物例如二甲酯的缩聚反应来制备。适合的二元醇具有式HO-R-OH,其中R是具有2至40,优选2至12个碳原子的二价的、支化的或未支化的脂族和/或环脂族基团。适合的二元羧酸具有通式HOOC-R’-COOH,其中R’是具有6至20,优选6至12个碳原子的二价芳族基团。
二元醇的实例是乙二醇、亚丙基二醇、1,4-丁二醇、2-丁烯二醇-1,4、1,6-己二醇、新戊二醇、1,4-环己烷二甲醇以及称为二聚二元醇的C36-二元醇。这些二元醇可以单独使用或作为二元醇混合物使用。
芳族二元羧酸例如是对苯二甲酸、间苯二甲酸、1,4-、1,5-、2,6-或2,7-萘二甲酸、联苯甲酸和二苯基醚-4.4’-二甲酸。最高达30摩尔%的这些二元羧酸、优选最高达10摩尔%可以被具有3至50个碳原子、优选具有6至40个碳原子的脂族或环脂族二元羧酸例如琥珀酸、己二酸、癸二酸、十二烷二酸或环己烷-1,4-二甲酸替代。
适合的聚酯的实例是聚对苯二甲酸乙二酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸丁二醇酯、聚2,6-萘二甲酸乙二醇酯、聚2,6-萘二甲酸丙二醇酯、聚2,6-萘二甲酸丁二醇酯、聚(1,4-二亚甲基环己烷对苯二甲酸酯)和聚(1,4-二亚甲基环己烷-2,6-萘二甲酸酯)。
这种聚酯的制备属于现有技术(DE-OSS 24 07 155、24 07 156;Ullmanns Encyclopdie der technischen Chemie,第4版,第19卷,第65页以下,Verlag Chemie,Weinheim,1980)。
已经证明特别适合的聚酯包含不超过300ppm、优选不超过150ppm、特别优选不超过100ppm和最优选不超过50ppm(在每种情况下以金属含量计)的催化酯交换反应和/或酯化反应的金属化合物或其转化产物,尽管对此的理由尚不清楚。
聚酯模制材料可以包含最多达约40重量%的其它热塑性塑料,特别是改善冲击强度的橡胶。此外,其还可包含对聚酯来说常规的助剂和添加剂,例如加工助剂、成核剂、嵌入或页状剥落的层状硅酸盐、结晶促进剂、光或热稳定剂、金属清除剂或配位剂;提高电导性的添加剂例如炭黑、碳纤维、钢纤维、纳米管等;增强添加剂例如玻璃纤维;或者颜料。
这些添加剂必须这样选择,即它们不提高或仅略微提高流过该聚酯模制材料的介质的电导性。如果使用水作为介质,那么电导性在90℃下应仅提高最大100μS/cm,优选最大50μS/cm,特别优选最大30μS/cm。如果使用水和甲醇的混合物(60∶40体积%),那么电导性在90℃下应仅提高最大80μS/cm,优选最大40μS/cm,特别优选最大20μS/cm。
通常该聚酯模制材料具有连续的聚酯相,其中优选地是整个基体由聚酯组成,并且常规组份分散在其中。
具体实施方式
在优选的实施方案中,该聚酯模制材料借助于上述提高电导性的添加剂而具有抗静电性,所以在输送可燃烧介质时,可以安全地将产生的静电荷散逸。在这种情况下,管路***和阳极正如在迄今为止使用的优质钢管路的情况一样,通过绝缘元件相互分开。
适合的聚酰胺是专业人员已知的,并且可以购得许多种类型。例如可以使用PA46、PA66、PA68、PA610、PA612、PA88、PA810、PA1010、PA1012、PA1212、PA6、PA7、PA8、PA9、PA10、PA11、PA12、基于此的共聚酰胺、支链的聚胺-聚酰胺共聚物以及它们的混合物。关于适合的均聚酰胺和共聚酰胺以及适合的聚胺-聚酰胺共聚物参阅EP-A-1216 826以及EP-A-1 216 823,其公开内容在此引为参考。
使用的聚酰胺模制材料可最多包括约50重量%的添加剂,这些添加剂选自赋与冲击强度的橡胶和/或常规助剂或填加料。
用于聚酰胺模制材料的赋与冲击强度的橡胶是现有技术。它们包含由不饱和官能化合物产生的官能基团,这些基团或者共聚在主链中或者接枝在主链上。最常使用的是被马来酸酐自由基接枝的EPM-或EPDM橡胶。正如在EP-A-0 683 210中所描述的,也可以将这种橡胶与未官能化的聚烯烃例如全同立构聚丙烯一起使用。
此外,该模制材料也可以包含少量的对于调整特定性能来说所需的助剂或填充料。对此的实例是增塑剂、颜料或填料(例如炭黑、二氧化钛、硫化锌、硅酸盐或碳酸盐)、加工助剂(例如蜡、硬脂酸锌或硬脂酸钙)、阻燃剂(例如氢氧化镁、氢氧化铝或氰脲酸蜜胺)、玻璃纤维、抗氧化剂、UV-稳定剂以及赋予产品抗静电性能或电导性的添加剂,例如碳纤维、石墨原纤、不锈钢纤维或导电炭黑。
在一种可能的实施方案中,该模制材料包含1至25重量%的增塑剂,特别优选是2至20重量%,最优选是3至15重量%。
增塑剂和其在聚酰胺中的应用是已知的。适合于聚酰胺的增塑剂的概述可参见Gchter/Müller,Kunststoffadditive,C.HanserVerlag,第2版,第296页。
适合于作为增塑剂的常规化合物例如是在醇组分中具有2至20个碳原子的对羟基苯甲酸的酯或在胺组分中具有2至12个碳原子的芳基磺酸的酰胺,优选苯磺酸的酰胺。
增塑剂可以是对羟基苯甲酸乙酯、对羟基苯甲酸辛酯、对羟基苯甲酸异十六酯、甲苯磺酸正辛酰胺、苯磺酸正丁酰胺或苯磺酸-2-乙基己酰胺。
层III或IV的聚烯烃例如是聚乙烯或聚丙烯。通常可以使用商业上可获得的每一种类型。这样例如可以是高、中或低密度的支链聚乙烯、LDPE、同分立构或无规立构均聚丙烯、丙烯与乙烯和/或丁烯-1的无规共聚物、乙烯-丙烯-嵌段共聚物等。这种聚烯烃也可以包含强化组分,例如EPM橡胶或EPDM橡胶或SEBS。此外,也可以包含常规助剂和添加剂。聚烯烃可以按照任何已知的方法制备,例如按照齐格勒-纳塔法,按照菲利普法,借助于金属茂或自由基方式。
可根据现有技术,使层IV的模制材料交联,以便改善机械性能,例如低温冲击强度、热成型稳定性或蠕变或渗透性。该交联例如通过辐射交联或借助于含硅烷基的聚烯烃模制材料的湿交联来进行。
层III的聚烯烃中包含的适合的官能基团例如是酸酐基团、N-酰基内酰胺基团、羧酸基团、环氧基团、噁唑啉基团、三烷氧基硅烷基团或羟基。这些官能基团可以通过适合单体与烯烃的共聚反应或者通过接枝反应而被引入。在接枝反应中,预先形成的聚烯烃以已知的方式与不饱和的官能单体以及有利地是与自由基发生剂在升温下反应。
EVOH早就是已知的。其是乙烯和乙烯醇的共聚物,并且有时也被称作EVAL。在共聚物中乙烯的含量通常是25至60摩尔%,特别是28至45摩尔%。在商业上可以获得各种类型。例如参阅公司出版物“Introduction to Kuraray EVALTM Resins”,Firma Kuraray EVALEurope的1.2/9810版本。
所述的EVOH一般是通过乙烯-乙酸乙烯酯-共聚物的皂化制备的。由于更好的加工性,根据本发明也可以使用部分皂化的乙烯-乙酸乙烯酯共聚物作为EVOH,其中皂化至少进行了60%,优选至少进行了80%,特别优选进行了至少90%。更好的可加工性也可以通过聚乙酸乙烯酯、乙烯-聚乙酸乙烯酯共聚物或聚酰胺的混合来获得。此外,该EVOH模制材料可以包含所有的现有技术已知的其它添加剂,例如层状硅酸盐。在该模制材料中EVOH的含量应至少是50重量%,优选至少是60重量%,特别优选至少是75重量%,最优选至少是90重量%。
用于层I与层II粘结的适合的粘结剂例如公开在EP-A-0 509211、EP-A-0 837 088以及EP-A-1 065 048中,其公开内容在此引为参考。
用于层I与层IV粘结的适合的粘结剂例如是聚酯和聚烯烃或官能化聚烯烃的共混物,如果需要加入相容剂,例如聚胺/聚酰胺共聚物(EP-A-1 065 048)。
用于层I与层V粘结的适合的粘结剂例如公开在EP-A-0 117 622中,其公开内容在此引为参考。此外,由层I中使用的聚酯以及与EVOH相容的聚酰胺(例如PA6、PA66或它们的共聚物)组成的共混物也是适合的,如果需要的话加入相容剂,例如聚酰胺-聚酯嵌段共聚物;备择地根据EP-A-1 065 048也可以使用聚胺-聚酰胺共聚物作为粘结剂,如果需要的话加入与EVOH相容的聚酰胺和/或在层I中使用的聚酯。
所有这些粘合剂均作为例如与其它层共挤出形成的独立层存在。
本发明的管路***或其单个元件可以以低的成本制造。此外其还具有轻的重量,这点在移动应用中是非常有利的。
本发明还涉及包括本发明元件的燃料电池***,例如用于驱动机动车。
Claims (6)
1.燃料电池的管路***的元件,其特征在于:与输送的介质接触的最内层由聚酯模制材料组成,此外,至少存在另一层,该层选自
a)由聚酰胺模制材料组成的层II,
b)由官能化的聚烯烃组成的模制材料制成的层III,
c)由聚烯烃模制材料制成的层IV,其中该聚烯烃是未官能化的,以及
d)由EVOH-模制材料制成的层V。
2.权利要求1的燃料电池管路***元件,其特征在于,该元件是多层管、贮备容器、连接件、转接器、过滤器、泵的构件或阀的构件。
3.上述权利要求之一的燃料电池管路***元件,其特征在于,所述的聚酯模制材料是以聚酯为基础的,所述的聚酯选自聚对苯二甲酸乙二酯、聚对苯二甲酸丙二醇酯、聚对苯二甲酸丁二醇酯、聚2,6-萘二甲酸乙二醇酯、聚2,6-萘二甲酸丙二醇酯、聚2,6-萘二甲酸丁二醇酯、聚(1,4-二亚甲基环己烷对苯二甲酸酯)和聚(1,4-二亚甲基环己烷-2,6-萘二甲酸酯)。
4.上述权利要求之一的燃料电池管路***元件,其特征在于,所述的聚酯模制材料具有抗静电性。
5.燃料电池***,其包括上述权利要求之一的元件。
6.用于驱动机动车的燃料电池***,其包括权利要求1至4之一的元件。
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DE2003116996 DE10316996A1 (de) | 2003-04-11 | 2003-04-11 | Leitungssystem für Fluide und Gase in einer Brennstoffzelle |
DE10316996.2 | 2003-04-11 |
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US (1) | US20040202908A1 (zh) |
EP (1) | EP1467428A1 (zh) |
JP (1) | JP2004319451A (zh) |
KR (1) | KR20040089541A (zh) |
CN (1) | CN1536702A (zh) |
AR (1) | AR043996A1 (zh) |
BR (1) | BRPI0401024A (zh) |
CA (1) | CA2463332A1 (zh) |
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DE102004048776A1 (de) * | 2004-10-07 | 2006-04-13 | Degussa Ag | Mehrschichtverbund mit EVOH-Schicht und Schutzschicht |
DE102004048777A1 (de) * | 2004-10-07 | 2006-04-13 | Degussa Ag | Mehrschichtverbund mit Polyesterschicht und Schutzschicht |
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2004
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US20040202908A1 (en) | 2004-10-14 |
BRPI0401024A (pt) | 2005-01-11 |
CA2463332A1 (en) | 2004-10-11 |
DE10316996A1 (de) | 2004-10-28 |
AR043996A1 (es) | 2005-08-17 |
JP2004319451A (ja) | 2004-11-11 |
EP1467428A1 (de) | 2004-10-13 |
KR20040089541A (ko) | 2004-10-21 |
MXPA04003196A (es) | 2004-10-14 |
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