CN1853066A - 绝热模制元件 - Google Patents
绝热模制元件 Download PDFInfo
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- CN1853066A CN1853066A CNA2004800265276A CN200480026527A CN1853066A CN 1853066 A CN1853066 A CN 1853066A CN A2004800265276 A CNA2004800265276 A CN A2004800265276A CN 200480026527 A CN200480026527 A CN 200480026527A CN 1853066 A CN1853066 A CN 1853066A
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- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
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- E04B1/80—Heat insulating elements slab-shaped
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
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- E04B1/803—Heat insulating elements slab-shaped with vacuum spaces included in the slab
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- F16L59/06—Arrangements using an air layer or vacuum
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明涉及一种包含硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料的模制元件。本发明的模制元件的特征在于它们含有至少一块真空绝热板。
Description
本发明涉及含有至少一块真空绝热板的用于绝热的模制品。
真空绝热元件,也称作真空绝热板,正越来越多地用于绝热。它们主要用于制冷电器的外壳、冷藏车货柜、冷藏箱(coolboxes)、冷藏室或长距离加热管。由于它们的低导热性,它们优于传统的绝热材料。因此,与封闭室硬质聚氨酯泡沫塑料相比,能源节省潜力通常为大约20-30%。
这种真空绝热元件通常包括绝热芯材,例如开放室硬质聚氨酯(PUR)泡沫塑料、开放室挤塑聚苯乙烯泡沫塑料、硅胶、玻璃纤维、聚合物材料的松散床、压制的细碎硬质或半硬PUR泡沫塑料、珍珠岩,该芯材包在气密膜中、抽空并与外界绝热地密封。压力应该低于100mbar。在这种真空下,根据芯材的结构和孔径大小,可以实现低于10mW/mK的绝热板导热性。
为了绝热,通常将绝热板加入待绝热的组件中并固定。上述绝热组件通常包括两层致密层,优选金属板或塑料(例如聚苯乙烯)。
EP 434225描述了制造绝热用组件的常规工业方法。为此,将真空绝热板粘结到至少一个侧壁上,并在剩余空腔内填入硬质聚氨酯泡沫塑料,否则其会起到热桥的作用。此外,对于在该组件的两个侧壁之间建立连接而言,用泡沫填充是必要的。
不可以忽略两个侧壁的一个,否则水蒸汽会扩散到硬质聚氨酯泡沫塑料中,这会造成导热性的极大提高。
这种方法和类似方法的缺点是,将真空绝热板固定到侧壁上是额外的操作步骤。因为无论如何必须避免对真空绝热板的损害,所以在组件中的安装和固定通常是手工进行的。
另一缺点在于在该程序中使用了两种具有不同绝热性能的绝热材料。因此,不能充分发挥真空绝热板的潜能。
本发明的一个目的是开发用于绝热的模制品,其具有非常低的导热性并且制造简单。
我们发现,通过用硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料完全包住真空绝热板,实现了该目的。
因此,本发明提供了一种模制品,其包含硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料并包含至少一块真空绝热板。
本发明进一步提供了包含硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料并包含至少一块真空绝热板的模制品的制造方法,其包括:
a)将至少一块真空绝热板加入模具中,
b)用硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料的原料组分填充该模具,
c)关闭模具,
d)在硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料固化之后从模具中取出模制品。
本发明还提供了本发明的模制品用于制造冷藏装置的用途。冷藏装置包括冰箱或冷柜之类的制冷电器、冷藏车、冷藏箱、冷藏室或长距离加热管。
为了制造本发明的模制品,可以使用常规已知的真空绝热板。它们可以如上所述制造:通常通过焊接或粘结将绝热芯材,例如开放室硬质聚氨酯(PUR)泡沫塑料、开放室挤塑聚苯乙烯泡沫塑料、硅胶、玻璃纤维、聚合物材料的松散床、压制的细碎硬质或半硬PUR泡沫塑料、珍珠岩,包在气密膜中,抽空并与外界绝热地密封。真空绝热板中的压力应该低于100mbar。为了长时间保持这种真空,通常还在真空绝热板中加入吸气剂材料,例如活性炭。在例如WO 97/36129或WO 99/61503中描述了这种真空绝热板。
用于制造本发明的模制品的具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料,也称作硬质聚氨酯整体泡沫塑料,它们的制造和使用在例如Kunststoffhandbuch,卷7“Polyurethane”,第三版1993,Carl HanserVerlag,Munich,Vienna,第7.4章中有描述。硬质致密聚氨酯与硬质聚氨酯整体泡沫塑料的不同之处在于在其配方中不使用发泡剂。
这些聚氨酯通常是通过使聚异氰酸酯,特别是二苯基甲烷4,4’-二异氰酸酯或其衍生物与短链聚醚醇在存在催化剂、发泡剂、需要时的交联剂和助剂和/或添加剂的情况下反应制得的。
这些聚氨酯通常用于制造外罩、体育设备(特别是滑雪设备)和用于家具。
至于用于制造硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料的原料化合物,可以提供下列细节:
作为聚异氰酸酯,原则上可以使用所有已知常规的在分子中含有至少两个异氰酸酯基团的脂族、特别是芳族异氰酸酯。通常使用二苯基甲烷二异氰酸酯或二苯基甲烷二异氰酸酯与多亚苯基多亚甲基多异氰酸酯的混合物制造硬质聚氨酯整体泡沫塑料。异氰酸酯可以作为纯净化合物使用或以改性形式使用。可以通过例如加入脲基甲酸酯、脲烷或异氰脲酸酯基团将聚异氰酸酯改性。
作为含有至少两个对异氰酸酯基团呈反应性的氢原子的化合物,优选使用聚醚醇和/或聚酯醇。
聚醚醇具有,特别地,2.5至5、优选2.5至4的官能度。聚醚醇的摩尔质量(Mw)优选为150至650,特别是200至600,按照DIN 53019测定,它们在25℃的粘度优选为250至7000mPas,特别是350至6500mPas。这些聚醚醇通过通常已知的方法制备,特别是通过将低碳环氧烷(优选环氧丙烷和/或环氧乙烷)加成到H-官能的原料物质上进行制备。优选的原料物质是3官能至5官能的醇或胺,例如甘油、三羟甲基丙烷、季戊四醇、山梨糖醇或1,2-乙二胺,或醇和/或胺的任何混合物。
作为聚酯醇,特别优选的是使用具有150至350毫克KOH/克的羟基数且在25℃的粘度(按照DIN 53019测定)为2000至10000mPas的那些聚酯醇。
它们可以按照已知方法通过使多官能羧酸与多官能醇反应来进行制备。多官能羧酸特别是,二羧酸和/或它们的衍生物,优选邻苯二甲酸、邻苯二甲酸酐或己二酸。所用多官能醇尤其是二醇,例如乙二醇及其更高级的同系物、丙二醇及其更高级的同系物、丁二醇或更高级的链烷二醇,特别是链烷链中含有最多10个碳原子的那些。为了提高聚酯醇的官能度,还可以使用少量的三官能或更高官能的醇。
通常可以只使用聚醚醇作为含有至少两个对异氰酸酯呈反应性的氢原子的化合物。在这种情况下可以使用一种聚醚醇或至少两种聚醚醇的混合物。
除了上述聚醚醇和聚酯醇,还可以使用增链剂和交联剂作为含有至少两个对异氰酸酯呈反应性的氢原子的化合物。这些是低分子H-官能化合物。这些化合物的分子量是62至上述聚醚醇和聚酯醇的分子量。所用增链剂通常是二醇,且所用交联剂通常是三官能醇和/或胺。
在是硬质聚氨酯整体泡沫塑料的情况下,在存在发泡剂、催化剂和需要时的助剂和/或添加剂的情况下进行本发明的方法。
对于发泡剂,可以例如使用对异氰酸酯呈反应性的水以去除二氧化碳。还可以使用物理发泡剂代替水,但优选与水结合使用。这些是对原料组分呈惰性并且在室温下通常是液体而在尿烷反应条件下气化的化合物。这些化合物的沸点优选低于110℃,特别是低于80℃。物理发泡剂还包括加入原料组分中或溶于其中的惰性气体,例如二氧化碳、氮或稀有气体。
在室温下是液体的化合物通常选自含有至少4个碳原子的链烷和环烷、二烷基醚、酮、缩醛、含有1至8个碳原子的氟代链烷和在烷基链中含有1至3个碳原子的四烷基硅烷,特别是四甲基硅烷。
物理发泡剂的例子是丙烷、正丁烷、异丁烷和环丁烷、正戊烷、异戊烷和环戊烷、环己烷、二甲基醚、甲基乙基醚、甲基丁基醚、甲酸甲酯、丙酮,以及可以在对流层中降解并因此不会破坏臭氧层的氟代链烷,例如三氟甲烷、二氟甲烷、1,1,1,3,3-五氟丁烷、1,1,1,3,3-五氟丙烷、1,1,12-四氟乙烷、二氟乙烷和七氟丙烷。所述物理发泡剂可以单独使用或者互相任意结合使用。
所用催化剂特别是能够强有力地促进异氰酸酯基团与对异氰酸酯基团呈反应性的基团的反应的化合物。特别优选的是使用有机金属化合物,尤其是有机锡化合物,例如有机酸的锡(II)盐。
还可以使用强碱性胺作催化剂。这种化合物的例子是脂族仲胺、咪唑、脒、三嗪和链烷醇胺。
这些催化剂可以根据需要单独使用或互相任意混合使用。
作为助剂和/或添加剂,使用本来就已知用于此目的的物质,例如表面活性剂、泡沫稳定剂、孔调节剂、填料(例如白垩或重晶石之类的矿物填料)、或中空微球、颜料、染料、阻燃剂、水解抑制剂、抗静电剂、制霉剂和抑菌剂。
为了制造本发明的模制品,将聚异氰酸酯与含有至少两个对异氰酸酯基团呈反应性的氢原子的化合物混合并加入模具中,该模具中预先已经加入了真空绝热板。在加入构成组分之后,将模具关闭并使聚氨酯固化。固化后,打开模具并取出模制品。
聚异氰酸酯与含有至少两个对异氰酸酯基团呈反应性的氢原子的化合物的反应优选以90至150、特别优选95至130的异氰酸酯指数进行。
工业中通常将含有至少两个对异氰酸酯基团呈反应性的氢原子的化合物与增链剂、交联剂、催化剂、发泡剂和助剂和/或添加剂结合以形成多元醇组分,并使其与聚异氰酸酯反应。然而,原则上还可以单独加入所有或一些上述原材料。
加入模具之前,反应组分的混合在最简单的情况下可以通过手动搅拌进行。然而,工业中通常用计量装置(通常是混料头)进行混合。这些装置通常是已知且市售的。
将混合物固化形成聚氨酯的温度优选为40至130℃。
用于本发明模制品的具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料通常具有200至800千克/立方米、优选200至700千克/立方米的密度。致密聚氨酯的密度优选为700至1200千克/立方米。
本发明的模制品可以制成各种应用所需的形状。从模具中取出之后不需要进行机械加工。真空绝热板优选完全被硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料包裹。
由于该模制品是自支承的,所以不需要象在传统冷藏容器中那样安装在金属或塑料外壳中。水蒸汽不能透过板周围的膜,因此不会有水蒸汽扩散到真空绝热板内部。
可以在模制过程中在模制品中制造门把手、铰链之类配件用的开孔,这样它们可容易装配以制造所需的绝热组件。
可以在至少一种构成组分中加入染料,由此将硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料着色。还可以在本发明的模制品的表面上提供表面涂层。
在本发明的优选具体实施方式中,侧面之一(优选内侧)可以是金属或塑料层。当内部的容易清洗性重要时,这特别优选。在这种情况下,将该层也置于模具中。这可以在加入构成组分之前或在关闭模具之前进行。
本发明的模制品具有非常低的导热性。它们制造简单,机械稳定而且重量低。
通过下列实施例阐述本发明。
实施例1
将尺寸为596×1196×36毫米的真空绝热板放入尺寸为600×1200×40毫米的模具中并适当地固定。然后将模具关闭并在该模具中加入3000克聚氨酯体系。
聚氨酯体系具有下列组成:
多元醇组分:下列材料的混合物:
19.36份(按重量计)羟基数为20毫克KOH/克的接枝多元醇,通过苯乙烯和丙烯腈在甘油生成的含有环氧乙烷和环氧丙烷的聚醚醇中的就地聚合制得,
25.97份(按重量计)羟基数为27毫克KOH/克的聚醚醇,通过将环氧乙烷和环氧丙烷加成到甘油上制得,
20.0份(按重量计)羟基数为750毫克KOH/克的聚醚醇,通过将环氧丙烷加成到乙二胺上制得,
10.0份(按重量计)二丙二醇,
10.0份(按重量计)二甘醇,
8份(按重量计)内部脱模剂,
3份(按重量计)Dabco33LV作为催化剂
6份(按重量计)黑糊,和
0.15份(按重量计)水;
异氰酸酯:来自BASF AG的Lupranat M20W
以110的指数进行反应。200秒后,从模具中取出该部件。
所用泡沫具有600-700克/升的自由发泡密度。
所得模制品具有致密外表层和多孔芯层。
Claims (8)
1.一种模制品,其包含硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料,并包含至少一块真空绝热板。
2.如权利要求1所述的模制品,其中真空绝热板完全被硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料包裹。
3.如权利要求1所述的模制品,其中具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料具有200至800千克/立方米的密度。
4.如权利要求1所述的模制品,其具有配件用的开孔。
5.如权利要求1所述的模制品,其是自支承的。
6.一种制造包含硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料并包含至少一块真空绝热板的模制品的方法,其包括:
a)将至少一块真空绝热板加入模具中,
b)用硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料的原料组分填充模具,
c)关闭模具,
d)在硬质致密聚氨酯或具有致密外表层和多孔芯层的硬质聚氨酯泡沫塑料固化之后从模具中取出模制品。
7.如权利要求1所述的模制品用于制造制冷电器的用途。
8.如权利要求1所述的模制品的用途,用于制造冰箱、冷柜、冷藏车、冷藏箱、冷藏室或长距离加热管。
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DE102013105819B4 (de) * | 2013-06-06 | 2019-01-17 | Kögel Trailer GmbH & Co. KG | Wandelement für einen Nutzfahrzeugaufbau, Nutzfahrzeugaufbau und Nutzfahrzeug mit einem derartigen Wandelement und Herstellungsverfahren |
AU2014276244B2 (en) * | 2013-06-07 | 2016-05-19 | Mitsubishi Electric Corporation | Heat insulating box body, refrigerator, and device including heat insulating box body |
WO2014196220A1 (ja) * | 2013-06-07 | 2014-12-11 | 三菱電機株式会社 | 冷蔵庫 |
CN103723379B (zh) * | 2014-01-11 | 2015-12-30 | 苏州安特实业有限公司 | 医疗药品用绝热冷藏箱 |
DE202014103892U1 (de) * | 2014-08-21 | 2015-11-25 | Rehau Ag + Co. | Verschlussanordnung |
KR20180071329A (ko) | 2015-10-19 | 2018-06-27 | 바스프 에스이 | Vip를 포함하는 샌드위치 구조체 및 이의 제조 방법 |
US10307938B2 (en) * | 2015-11-17 | 2019-06-04 | Great Plains Coatings, Inc. | Chemical resistant composite support pad mold and method of manufacturing the support pad |
JP7345138B2 (ja) * | 2017-12-22 | 2023-09-15 | パナソニックIpマネジメント株式会社 | 真空断熱材を備えた断熱構造体、ならびに、それを用いた家電製品、住宅壁および輸送機器 |
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DE4115456A1 (de) * | 1991-05-11 | 1992-11-12 | Basf Ag | Verfahren zur herstellung von fluorchlorkohlenwasserstoff freien, urethangruppen enthaltenden formkoerpern mit einem zelligen kern und einer verdichteten randzone |
JPH0771867A (ja) * | 1993-09-03 | 1995-03-17 | Fujitsu General Ltd | 断熱材ユニットとそれを利用した断熱箱体 |
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-
2003
- 2003-09-15 DE DE2003142859 patent/DE10342859A1/de not_active Withdrawn
-
2004
- 2004-09-08 EP EP04764960A patent/EP1664616A1/de not_active Withdrawn
- 2004-09-08 KR KR1020067005159A patent/KR20060076296A/ko not_active Application Discontinuation
- 2004-09-08 WO PCT/EP2004/010017 patent/WO2005026605A1/de active Search and Examination
- 2004-09-08 MX MXPA06002429A patent/MXPA06002429A/es unknown
- 2004-09-08 JP JP2006525757A patent/JP2007506041A/ja not_active Withdrawn
- 2004-09-08 US US10/571,915 patent/US20080280120A1/en not_active Abandoned
- 2004-09-08 CN CNA2004800265276A patent/CN1853066A/zh active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103153572A (zh) * | 2010-09-22 | 2013-06-12 | 巴斯夫欧洲公司 | 真空隔热板在冷却装置中的固定 |
CN103153572B (zh) * | 2010-09-22 | 2015-08-05 | 巴斯夫欧洲公司 | 真空隔热板在冷却装置中的固定 |
CN102748558A (zh) * | 2012-07-16 | 2012-10-24 | 苏州宏久航空防热材料科技有限公司 | 一种圆弧形真空绝热复合板及其制作方法 |
CN105393073A (zh) * | 2013-06-07 | 2016-03-09 | 三菱电机株式会社 | 隔热箱体和冰箱 |
CN105393073B (zh) * | 2013-06-07 | 2019-03-08 | 三菱电机株式会社 | 隔热箱体和冰箱 |
CN113370448A (zh) * | 2014-02-06 | 2021-09-10 | 巴斯夫欧洲公司 | 用于储存容器的绝热组件及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
WO2005026605A1 (de) | 2005-03-24 |
JP2007506041A (ja) | 2007-03-15 |
DE10342859A1 (de) | 2005-04-21 |
US20080280120A1 (en) | 2008-11-13 |
KR20060076296A (ko) | 2006-07-04 |
EP1664616A1 (de) | 2006-06-07 |
MXPA06002429A (es) | 2006-06-20 |
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