CN101006233A - 由硬质聚氨酯泡沫制得的复合元件 - Google Patents
由硬质聚氨酯泡沫制得的复合元件 Download PDFInfo
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- CN101006233A CN101006233A CNA200580028050XA CN200580028050A CN101006233A CN 101006233 A CN101006233 A CN 101006233A CN A200580028050X A CNA200580028050X A CN A200580028050XA CN 200580028050 A CN200580028050 A CN 200580028050A CN 101006233 A CN101006233 A CN 101006233A
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Classifications
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- E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
- E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
- E04C2/04—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of concrete or other stone-like material; of asbestos cement; of cement and other mineral fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0004—Use of compounding ingredients, the chemical constitution of which is unknown, broadly defined, or irrelevant
- C08J9/0009—Phase change materials
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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
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
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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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/30—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being formed of particles, e.g. chips, granules, powder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
- E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
- E04C2/10—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products
- E04C2/20—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products of plastics
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
- E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
- E04C2/26—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups
- E04C2/284—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating
- E04C2/296—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating composed of insulating material and non-metallic or unspecified sheet-material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Abstract
本发明涉及一种由硬质聚氨酯泡沫和两个外层构成的复合元件,其中至少一个外层是用微胶囊改性的模制品,并且该微胶囊包含聚合物作为胶囊壁和主要包含潜热蓄积材料的胶囊芯。
Description
本申请涉及由硬质聚氨酯泡沫和两个外层构成的复合元件。
由硬质聚氨酯泡沫构成的复合元件已知为夹层元件,它们不仅用作家用建筑的结构元件,而且还用作工业建筑的结构元件,以用于工业建筑的立面和屋顶,以及用作冷藏建筑、隔断门、便携式办公室设施或住宅拖车建筑的结构元件,其中所述复合元件的广泛用途基于它们非常好的隔热性能。它们可用于生产能量最优化的结构体。然而,它们的低密度意味着,它们的建筑物关于温度峰几乎不具有缓冲能力,并且受到非常迅速的加热或冷却,得到令人不满意的内部大气条件。
在夏天,结构体的物质在白天蓄积流入的热量,因此在理想情况下保持内部温度恒定。然后,蓄积的热量在更冷的夜间条件下释放回外部大气中。如果甚至在夏天要在不开空调的情况下也要实现舒适的温度和湿度,因此,建筑的热物质是必不可少的。然而,由夹层元件构成的建筑缺乏任何那些大的热物质。
近些年,已经研究了作为组合建筑材料的新形式的潜热蓄积体。它们的作用方式基于在固/液相转变的过程中产生的焓,这涉及在恒定温度下能量吸收或释放到环境中。它们因此可以用于在特定温度范围内保持恒定的温度。由于取决于温度,潜热蓄积材料也可以为液体,因此它们不能直接用作建筑材料,因为会担心它们排放到内部大气中或担心它们与建筑材料分离。
DE-A-101 39 171描述了微胶囊化潜热蓄积材料在纸面石膏板中的应用。
早期的美国申请序列号60/573420教导了微胶囊化潜热蓄积材料在刨花板中的应用。
本发明的目的是改进由硬质聚氨酯泡沫构成的复合元件,其改进方式使得由复合元件生产的建筑具有更好的大气条件。
上述目的通过由硬质聚氨酯泡沫和两个外层构成的复合元件得以实现,其中至少一个外层是用微胶囊改性的模制品,并且该微胶囊包含聚合物作为胶囊壁和主要由潜热蓄积材料组成的胶囊芯。
使用的外层可以是具有足够强度的任何所需片状材料的层。优选的外层是由例如熟石膏、含塑料或含木素纤维素的材料构成的面板,该面板适于在其容积内粘合足量的潜热蓄积材料。优选的是其中至少一个外层是由含木素纤维素的材料构成的改性模制品或者是基于熟石膏的改性模制品的复合元件。这类模制品描述于DE-A-101 39 171、DE-A-101 43 612和早期的美国申请序列号60/573420中。
未改性的外层也称作朝外的外层,它通常在建筑的外部,它可以由用于这些复合元件的常见的通常耐候的材料构成。外层优选是金属箔和/或金属板,塑料板和/或塑料箔,或者相应的织物等。不必要的是,外层具有仿形轮廓。它还可以是光滑的,或者是印花、仿形或模制板(例如波形瓦效果)。
对于内部应用,例如在隔断墙的情况下,这类复合元件还可以由在两侧通过使用潜热蓄积体改性的模制品构成。
存在于根据本发明改性的模制品中的微胶囊是这样的颗粒,其胶囊芯主要并且超过90重量%由潜热蓄积材料构成并且聚合物作为胶囊壁。胶囊芯这里是固体或液体,这由温度决定。胶囊的平均尺寸(借助光散射得到的数均)为0.5-100μm,优选1-80μm,特别是1-50μm。胶囊芯与胶囊壁的重量比通常为50∶50-95∶5。优选芯/壁比例为70∶30-90∶10。
潜热蓄积材料定义为在意图传热的温度范围内具有相转变的物质。潜热蓄积材料优选在-20至120℃的温度范围内具有固/液相转变。潜热蓄积体通常是有机、优选亲脂性物质。
可以对合适物质提及的实例是:
-脂族烃化合物,如支化或优选线性的饱和或不饱和C10-C40烃,例如正十四烷、正十五烷、正十六烷、正十七烷、正十八烷、正十九烷、正二十烷、正二十一烷、正二十二烷、正二十三烷、正二十四烷、正二十五烷、正二十六烷、正二十七烷、正二十八烷,以及还有环状烃,例如环己烷、环辛烷、环癸烷;
-芳族烃化合物,如苯、萘、联苯、邻三联苯、正三联苯,C1-C40烷基取代的芳族烃,如十二烷基苯、十四烷基苯、十六烷基苯、己基萘或癸基萘;
-饱和或不饱和C6-C30脂肪酸,如月桂酸、硬脂酸、油酸或二十二烷酸,优选由癸酸与例如肉豆蔻酸、棕榈酸或月桂酸组成的共熔混合物;
-脂肪醇,如月桂醇、硬脂醇、油醇、肉豆蔻醇或十六烷基醇,混合物,如椰子脂肪醇,以及通过α-烯烃的醛化反应和其它反应得到的称作羰基合成醇的醇;
-C6-C30脂肪胺,如癸基胺、十二烷基胺、十四烷基胺或十六烷基胺;
-脂,如脂肪酸的C1-C10烷基酯,例如棕榈酸丙基酯、硬脂酸甲酯或棕榈酸甲酯,或者优选它们的共熔混合物,或肉桂酸甲酯;
-天然或合成蜡,如褐煤酸蜡、褐煤酯蜡、巴西棕榈蜡、聚乙烯蜡、氧化蜡、聚乙烯基醚蜡、乙烯/乙酸乙烯酯蜡或来自Fischer-Tropsch方法的硬质蜡;
-卤化烃,如氯代石蜡、溴代十八烷、溴代十五烷、溴代十九烷、溴代二十烷、溴代二十二烷。
这些物质的混合物也是适合的,只要所得熔点不降低到所需范围以外,并且只要混合物的熔融热不变得太小以至于没有帮助。
作为举例,有利的是使用纯正链烷烃,纯度大于80%的正链烷烃,或者作为工业馏出物产生的并且本身可以市购的链烷烃混合物。
还可能有利的是,将可溶于形成胶囊芯的物质中的化合物添加到那些物质中,以抑制在非极性物质的情况下有时发生的凝固点的降低。有利的是,如US-A 5 456 852中所述,使用熔点比实际的芯物质的熔点高20-120K的化合物。合适的化合物是上面作为亲脂性物质提及的呈脂肪酸、脂肪醇、脂肪胺以及脂族烃化合物形式的物质。这些物质的用量基于胶囊芯为0.1-10重量%。
潜热蓄积材料根据蓄热体所要求的温度范围进行选择。作为举例,对于在温度和湿度的中等条件下在建筑材料中的蓄热体,优选使用其固/液相转变在0-60℃的温度范围内的潜热蓄积材料。因此,通常选择转变温度为15-30℃的各物质或混合物用于内部应用。
优选的潜热蓄积材料是脂族烃,尤其优选上面作为例子列出的材料。特别优选具有16、17或18个羰原子的脂族烃,以及还有这些烃的混合物。
用于胶囊壁的聚合物原则上可以包括任何已知用于复印纸张用微胶囊的材料。作为举例,可以根据描述于GB-A 870476、US 2,800,457、US 3,041,289中的方法使用其它聚合物将潜热蓄积材料包封于明胶中。
由于高度耐老化而优选的壁材料是热固性聚合物。这里,热固性壁材料是具有高交联度并因此在高温下不软化而是发生分解的那些材料。合适的热固性壁材料的实例是高度交联的甲醛树脂,高度交联的聚脲、高度交联的聚氨酯和高度交联的甲基丙烯酸酯聚合物。
甲醛树脂是甲醛与如下化合物或其混合物的反应产物:
-三嗪类化合物,例如蜜胺,
-氨基甲酰胺,如尿素,
-酚类,例如苯酚、间甲酚和间苯二酚,
-氨基和酰氨基化合物,如苯胺、对甲苯磺酰胺、亚乙基脲和胍。
用作胶囊壁材料的优选甲醛树脂是尿素-甲醛树脂、尿素-间苯二酚-甲醛树脂、尿素-蜜胺树脂和蜜胺-甲醛树脂。还优选的是这些甲醛树脂的C1-C4烷基醚,尤其是其甲基醚,以及与这些甲醛树脂的混合物。特别优选蜜胺-甲醛树脂和/或它们的甲基醚。
在由复印纸张已知的方法中,树脂以预聚物形式使用。该预聚物仍旧可溶于水相中,并且在缩聚过程中迁移到相边界并包围油滴。用甲醛树脂微胶囊化的方法是熟知的,并且例如描述于EP-A-562 344和EP-A-974 394中。
由聚脲和聚氨酯构成的胶囊壁通常由复印纸张已知。该胶囊壁通过含NH2或OH的反应物与二-和/或多异氰酸酯反应来产生。合适的异氰酸酯的实例是亚乙基二异氰酸酯、四亚甲基1,4-二异氰酸酯、六亚甲基1,6-二异氰酸酯以及甲苯2,4-和2,6-二异氰酸酯。还可以提及多异氰酸酯,如具有缩二脲结构的衍生物、聚脲酮亚胺和异氰脲酸酯。可以使用的反应物是:肼、胍和其盐,羟胺、二-和多胺,以及氨基醇。这些界面加聚方法例如公开于US 4,021,595、EP-A 0 392 876和EP-A 0 535 384中。
优选其胶囊壁是高度交联的甲基丙烯酸酯聚合物的微胶囊。这里,交联度通过使用基于整个聚合物为10重量%的交联剂实现。
在优选微胶囊中的成壁聚合物由30-100重量%、优选30-95重量%的一种或多种丙烯酸和/或甲基丙烯酸的C1-C24烷基酯作为单体I组成。该聚合物还可以包含至多80重量%、优选5-60重量%、尤其10-50重量%的共聚的不溶于或微溶于水的双或多官能单体作为单体II。这里,该聚合物还可包含至多40重量%、优选至多30重量%的其它共聚单体III。
合适的单体I是丙烯酸和/或甲基丙烯酸的C1-C24烷基酯。特别优选的单体I是丙烯酸的甲基酯、乙基酯、正丙基酯和正丁基酯,和/或相应的甲基丙烯酸酯。优选丙烯酸的异丙基酯、异丁基酯、仲丁基酯和叔丁基酯,以及相应的甲基丙烯酸酯。还可以提及甲基丙烯腈。通常优选甲基丙烯酸酯。
合适的单体II是不溶于或微溶于水但是在亲脂性物质中具有良好到有限溶解性的双-或多官能单体。微溶指的是溶解度于20℃下小于60 g/l。双-或多官能单体是具有至少2个非共轭烯属双键的化合物。通常优选的单体是在聚合过程中产生胶囊壁的交联的二乙烯基和多乙烯基单体。
优选的双官能单体是二醇与丙烯酸或甲基丙烯酸的二酯,以及这些二醇的二烯丙基醚和二乙烯基醚。
优选的二乙烯基单体是二丙烯酸乙二醇酯、二乙烯基苯、二甲基丙烯酸乙二醇酯、二甲基丙烯酸1,3-丁二醇酯、甲基烯丙基甲基丙烯酰胺以及甲基丙烯酸烯丙基酯。特别优选二丙烯酸丙二醇酯、二丙烯酸丁二醇酯、二丙烯酸戊二醇酯和二丙烯酸己二醇酯,或者相应的甲基丙烯酸酯。
优选的多乙烯基单体是三羟甲基丙烷三丙烯酸酯和三羟甲基丙烷三甲基丙烯酸酯、季戊四醇三烯丙基醚和季戊四醇四丙烯酸酯。
可使用的单体III是其它单体,优选单体IIIa,如苯乙烯、α-甲基苯乙烯、β-甲基苯乙烯、丁二烯、异戊二烯、乙酸乙烯酯、丙酸乙烯酯和乙烯基吡啶。
特别优选水溶性单体IIIb,如丙烯腈、甲基丙烯酰胺、丙烯酸、甲基丙烯酸、衣康酸、马来酸、马来酸酐、N-乙烯基吡咯烷酮、丙烯酸2-羟基乙基酯、甲基丙烯酸2-羟基乙基酯和丙烯酰氨基-2-甲基丙烷磺酸。除了这些单体,可特别提及N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、甲基丙烯酸二甲基氨基乙基酯和甲基丙烯酸二乙基氨基乙基酯。
适合根据本发明使用的微胶囊可以通过称之谓就地聚合的聚合制备。
优选的微胶囊及其生产公开于EP-A-457 154,DE-A-10 139 171,DE-A-102 30 581,EP-A-1 321 182中,这些文献在此特地引入作为参考。例如,按照如下制备微胶囊:使用单体、自由基引发剂、保护性胶体和待包封的亲脂性物质,并由这些制备稳定的水包油乳液,在该乳液中微胶囊作为分散相存在。于是,通过加热引发单体的聚合,并优选通过进一步的温度升高进行控制,由此所得聚合物形成包围亲脂性物质的胶囊壁。
聚合通常在20-100℃、优选40-80℃的温度下进行。分散温度和聚合温度自然应该高于亲脂性物质的熔点。
一旦已经达到最终温度,有利的是继续聚合不超过例如2小时的时间,以便降低残余单体含量。在实际聚合反应达到90-99重量%的转化率之后,通常有利的是,基本上除去微胶囊水分散体中的气味剂,如残余单体和其它挥发性有机成分。这可以以本身已知的方式物理地通过蒸馏除去(尤其通过蒸汽蒸馏)或通过用惰性气体汽提来实现。还可使用描述于WO 9924525中的化学方法,有利地通过如DE-A-4 435 423、DE-A-4419518和DE-A-4435422中所述的氧化还原体系引发的聚合来实现。
该方法可以产生平均粒度为0.5-100μm的微胶囊,这里,粒度可以以本身已知的方式借助剪切力、搅拌速率、保护性胶体及其浓度来调节。
优选的保护性胶体是水溶性聚合物,因为这些胶体会将水的表面张力由最大值73mN/m降至45-70mN/m,因此确保形成封闭的胶囊壁以及优选粒度为1-30μm、优选3-12μm的微胶囊。
微胶囊通常在至少一种有机保护性胶体存在下进行生产,该胶体可以是阴离子性的或中性的。还可以一起使用阴离子性和非离子性保护性胶体。优选使用无机保护性胶体,合适的话以与有机保护性胶体的混合物使用。
中性有机保护性胶体是纤维素衍生物,如羟乙基纤维素、羧甲基纤维素和甲基纤维素,聚乙烯基吡咯烷酮,乙烯基吡咯烷酮共聚物,明胶,阿拉伯胶,黄原胶,藻酸钠,酪蛋白,聚乙二醇,优选聚乙烯醇和部分水解的聚乙酸乙烯酯。
合适的阴离子性保护性胶体是聚甲基丙烯酸,丙烯酸磺乙基酯的和甲基丙烯酸磺乙基酯的共聚物,丙烯酸磺丙基酯的和甲基丙烯酸磺丙基酯的共聚物,N-磺乙基马来酰亚胺的共聚物,2-丙烯酰氨基-2-烷基磺酸的共聚物,苯乙烯磺酸的共聚物以及乙烯基磺酸的共聚物。
优选的阴离子性保护性胶体是萘磺酸和萘磺酸-甲醛缩合物,尤其是聚丙烯酸和苯酚磺酸-甲醛缩合物。
阴离子性保护性胶体的通常用量基于乳液的水相为0.1-10重量%。
优选称作Pickering体系的无机保护性胶体,该胶体允许通过非常细的固体颗粒实现稳定化,并且可分散于水中但不溶于水中,或者不溶于水中且不可分散于水中,但是可以被亲脂性物质润湿。
保护性胶体的作用模式及其应用描述于EP-A-1 029 018和EP-A-1 321182中,这些文献的内容特地引入此处作为参考。
Pickering体系可以单独由固体颗粒组成,或者也可以包含改进颗粒在水中的分散性或改进亲脂相对于颗粒的润湿性的助剂。
无机固体颗粒可以是金属盐,例如钙、镁、铁、锌、镍、钛、铝、硅、钡或锰的盐、氧化物和氢氧化物。可以提及氢氧化镁、碳酸镁、氧化镁、草酸钙、碳酸钙、碳酸钡、硫酸钡、二氧化钛、氧化铝、氢氧化铝和硫化锌。还可以提及硅酸盐、膨润土、羟基磷灰石和水滑石。特别优选细颗粒硅石,以及焦磷酸镁和磷酸三钙。
Pickering体系可以先添加到水相中,或者添加到搅拌的水包油乳液中。一些细的固体颗粒通过沉淀制备,这如EP-A-1 029 018和EP-A-1 321182中所述。
细颗粒硅石当分散于水中时,可以呈细固体颗粒的形式。然而,也可以使用硅石在水中的胶状分散体。胶状分散体是硅石的碱性含水混合物。在碱性pH范围内,颗粒是在水中稳定的溶胀颗粒。对于将这些分散体用作Pickering体系,有利的是在水包油乳液阶段过程中使用酸将pH调节为2-7。
无机保护性胶体的通常用量基于水相为0.5-15重量%。
中性有机保护性胶体的通常用量基于水相为0.1-15重量%,优选0.5-10重量%。
产生稳定的水包油乳液的分散条件的选择优选遵循这样的已知方法,以使得油滴具有所需微胶囊的尺寸。
优选本发明复合元件的至少一个外层是由含木素纤维素的材料构成的改性模制品。微胶囊可以引入到经常用于由含木素纤维素的材料构成的模制品用的粘合剂树脂中。
现有技术的含木素纤维素的材料的实例是:来自圆木或劈木材加工的小木块,来自锯木机或来自镶木工艺的废料,来自刨制或削制工艺的刨花,以及其它含木素纤维素的材料,例如蔗渣、亚麻片、棉梗、黄麻、剑麻、稻草、椰子纤维、橡胶纤维、大麻和软木。特别优选木纤维或小木块。这些原材料可以呈颗粒、粉末或优选刨花、纤维和/或碎屑形式。
可以提及的优选的粘合剂树脂是氨基塑料树脂、酚类树脂、异氰酸酯树脂和聚羧酸树脂。
可以使用的氨基塑料树脂是基于尿素或蜜胺的甲醛缩合物的粘合剂。它们可以以水溶液或粉末形式都以商品名Kaurit和Kauramin(生产商:BASF)市购,并且包含尿素-和/或蜜胺-甲醛预缩合物。可以包含其它成分如苯酚或其它醛类的混合缩合物和缩合物是常规的。合适的氨基塑料树脂和酚类树脂是尿素-蜜胺-甲醛缩合物、蜜胺-尿素-甲醛-苯酚缩合物、苯酚-甲醛缩合物、苯酚-间苯二酚-甲醛缩合物、尿素-甲醛缩合物和蜜胺-甲醛缩合物,以及这些树脂的混合物。它们的制备和用途是熟知的。起始原料通常预缩合至200-500mPas的粘度(基于66重量%强度的树脂溶液)。
优选尿素-和/或蜜胺-甲醛树脂,尤其是摩尔比为1摩尔尿素对1.1-1.4摩尔甲醛的那些。
在加工氨基塑料树脂的过程中,将可溶的和可熔合的氨基塑料预缩合物转化为不可溶的和不熔合的产物。在该程序(称作固化)中,已知预缩合物的连续交联开始发生,并且由硬化剂加速。
可使用的硬化剂是本领域熟练技术人员已知的为如下树脂所用的硬化剂:尿素-、苯酚-和/或蜜胺-甲醛树脂,例如具有酸性反应和/或消去酸的化合物,例如铵盐或胺盐。硬化剂在粘合剂树脂液中的比例基于液体树脂内容物通常为1-5重量%。
合适的异氰酸酯树脂是基于亚甲基二苯基异氰酸酯(MDI)的任何熟悉树脂。它们通常由已知为预缩合物的混合物构成,该混合物由单体材料、聚合物材料和低聚二异氰酸酯组成,这些预缩合物能够与纤维素、木素和木材中存在的湿气反应。由其生产的模制品的树脂含量基于模制品通常为3-5重量%。
合适的异氰酸酯树脂的实例可作为Lupranat品级(Elastogran)市购。
其它合适的粘合剂树脂包括这样的聚羧酸树脂,该树脂包含:
A)通过自由基聚合获得的并且由5-100重量%、优选5-50重量%的烯属不饱和酸酐或者其羧酸基可形成酸酐基团的烯属不饱和二元羧酸(单体a))以及0-95重量%、优选50-95重量%的不同于单体a)的单体b),以及
B)具有至少两个羟基的链烷醇胺。
这类树脂描述于EP-A-882 093中,该文献特地引入此处作为参考。
特别优选的是包含马来酸和/或马来酸酐作为单体a)的聚合物。
优选的单体b)是丙烯酸、甲基丙烯酸、乙烯、丙烯、丁烯、异丁烯环戊烯、甲基.乙烯基醚、乙基.乙烯基醚、丙烯酰胺、2-丙烯酰氨基-2-甲基丙磺酸、乙酸乙烯酯、苯乙烯、丁二烯、丙烯腈或这些的混合物。特别优选丙烯酸、甲基丙烯酸、乙烯、丙烯酰胺、苯乙烯和丙烯腈,或这些的混合物。
特别优选的是其中单体b)包含至少一种C3-C6单羧酸、优选丙烯酸作为单体b)的那些材料。
所述聚合物可以通过常规的聚合方法,例如通过本体、乳液、悬浮、分散、沉淀或溶液聚合而制备。常规设备用于所有聚合方法,例如搅拌釜、搅拌釜级联、高压釜、管式反应器或捏合机。如本领域熟练技术人员熟悉的那样,这些操作在排除空气的情况下进行。使用的优选方法是溶液或乳液聚合。该聚合在水中进行,合适的话还含有不超过60重量%比例的醇或二醇作为溶剂或稀释剂。
如果聚合在水溶液中或在稀释体系中进行,则可以在聚合之前或聚合过程中用碱部分或全部中和烯属不饱和羧酸。可以使用的碱的实例是碱金属化合物、碱土金属化合物、氨、伯胺、仲胺或叔胺如二乙醇胺或三乙醇胺,或者多元胺。
特别优选的是,在聚合之前或在聚合过程中不中和烯属不饱和羧酸。还优选的是,在聚合之后只加入链烷醇胺B)中和剂。
可以使用各种连续或分批技术进行聚合反应。通常的方法包括:形成一部分单体的初始投料,这合适的话在合适的稀释剂或溶剂中以及合适的话在乳化剂、保护性胶体或其它助剂存在下,将该初始投料惰性化,以及升高温度,直到已经达到所需聚合温度。在限定时间内,计量加入自由基引发剂、其它单体和其它助剂,如调节剂或交联剂,合适的化每种情况下都在稀释剂中。
聚合物A)优选呈水分散体或水溶液形式,具有的固含量优选为10-80重量%,尤其是40-65重量%。
作为组分B),使用具有至少两个OH基团的链烷醇胺,其实例是二乙醇胺、三乙醇胺、二异丙醇醇、三异丙醇胺、甲基二乙醇胺、丁基二乙醇胺和甲基二异丙醇胺。优选三乙醇胺。
为了制备聚羧酸树脂,聚合物A)和链烷醇胺B)相互的优选使用比例使得组分A)的羧基和组分B)的羟基的摩尔比为20∶1-1∶1,优选8∶1-5∶1,特别优选5∶1-1.7∶1(这里,对于计算,酸酐基团被认为具有两个羧基)。
制备聚羧酸树脂的实例是将链烷醇胺简单添加到聚合物A)的水分散体或水溶液中。
微胶囊可以以各种方式并且在生产过程中的各种点加入到由木纤维或木刨花和粘合剂组成的并用作模制品的基础的混合物中。
微胶囊引入到粘合剂组合物中的形式可以为分散体形式,优选粉末形式。这里,微胶囊的引入量基于模制品为2-30重量%,优选5-15重量%。然而,也可以在第一步中将微胶囊与含木素纤维素的材料一起干燥,然后用粘合剂树脂将它们热固化。
优选的模制品包含含木素纤维素的材料以及基于模制品的重量按照固体计算为5-20重量%的粘合剂树脂和2-30重量%的微胶囊。
基于100重量%的粘合剂组合物,合适的粘合剂组合物包含以固体计算为40-65重量%、尤其50-60重量%的粘合剂树脂,5-40重量%、优选10-35重量%、尤其20-30重量%的微胶囊,以及合适的话,水。
连同用于由含木素纤维素的材料构成的模制品的粘合剂树脂,还可以使用常规助剂和添加剂,如上述硬化剂、缓冲剂、杀虫剂、杀真菌剂、填料、疏水剂如硅油、石蜡、蜡、脂肪酸皂、保水剂、润湿剂和阻燃剂,如硼酸盐和氢氧化铝。
改性模制品尤其是是板材。取决于所用的含木素纤维素的刨花的尺寸,可以分为OSB(定向结构板)、刨花板和中密度纤维板(MDF)和高密度纤维板(HDF)。粘合剂组合物优选用于木刨花材料,尤其是板材。
含木素纤维素的材料可以直接涂覆上微胶囊或粘合剂组合物。在本方法的一个变型中,将含木素纤维素的材料与粘合剂组合物混合,将该混合物热固化,这里的粘合剂组合物包含40-95重量%粘合剂树脂,5-40重量%的其中聚合物作为胶囊壁和胶囊芯主要由潜热蓄积材料构成的微胶囊,以及0-20重量%的水。
在本方法的一个变型中,基于含木素纤维素的材料和粘合剂组合物的总量,将9-30重量%、12-20重量%的含水粘合剂组合物添加到含木素纤维素的材料中。
含水粘合剂组合物的粘度优选调节(特别在生产由木纤维或木刨花粒组成的模制品的情况下)至10-10 000mPas,特别优选至50-1500mPas,非常特别优选至100-1000mPas(DIN 53019,旋转型粘度计,于41秒-1)。
由含木素纤维素的材料和由粘合剂组合物组成的混合物可以例如于10-150℃下预先干燥,然后于例如50-300℃、优选100-250℃、特别优选140-225℃的温度下和通常2-200巴、优选5-100巴、特别优选20-50巴的压力下压制,得到模制品。出人意料的是,尽管模塑温度高和压力高,但是微胶囊不发生破裂,尽管模塑温度大部分高于胶囊壁材料的软化点。
粘合剂组合物特别适合生产基于原木的材料,如刨花板和木纤维板(参见Ullmanns Encyclopidie der technischen Chemie[Ullmann工业化学百科全书],第四版,1976,卷12,709-727),这些板可通过粘合粘结碎木如木刨花和木纤维而生产。
刨花板的生产是熟知的,并且例如描述于H.J.Deppe,K.ErnstTaschenbuch der Spanplattentechnik[刨花板技术手册],第二版,VerlagLeinfelden 1982中。
连续混合器用于刨花板生产,以将粘合剂施用于预先干燥的刨花上。在分开的混合器中通过不同方法将粘合剂主要施用于不同刨花部分,然后将各部分分开(多层板)或一起给料。微胶囊可以以水溶液与粘合剂一起或与粘合剂分开添加到在连续混合器中的干燥器上游的刨花中,或者在施用粘合剂的过程中添加。还可以使用前述两种方法的组合。
优选使用其平均颗粒厚度为0.1-2mm、尤其0.2-0.5mm并且包含少于6重量%水的刨花。以最大均匀度将粘合剂组合物施用于木刨花,例如通过将细分散的粘合剂组合物喷雾到木刨花上。
然后,将涂覆有粘合剂的木刨花铺展开,得到具有最大表面均匀度的层,该层的厚度取决于成品刨花板的所需厚度。合适的话,将该散开层趁冷预先压紧,并在例如100-250℃、优选140-225℃的温度下通过施加通常10-750巴的压力压制,得到二维稳定的板。所需的压制时间可在宽范围内变化,通常为15秒至30分钟。
由粘合剂生产中密度木纤维(MDF)所需要的合适质量的木纤维可以由无树皮的木屑通过在特定的磨中或在精磨机中于约180℃的温度下研磨来生产。
为了生产MDF板和HDF板,将粘合剂施用于在精磨机下游的喷吹管(Blowline)中的纤维。对于粘合剂的施用,通常将木纤维通过空气气流流化,将粘合剂组合物注射到所得的纤维料流中(喷吹管法)。然后,使带有所施用粘合剂的纤维通过干燥器,纤维在该干燥器中于7-13重量%的湿气水平下干燥。偶尔,首先干燥纤维,然后在特定的连续混合器中施用粘合剂。还可行的是喷吹管法施用和粘合剂施用的联合。微胶囊可以在喷吹管中以水溶液与粘合剂一起或与粘合剂分开加入到纤维中。基于干燥物或固体物,木纤维与粘合剂组合物的比例通常为40∶1-3∶1,优选20∶1-4∶1。带有所施加的粘合剂的纤维在纤维料流中于例如130-180℃的温度下干燥,铺展得到纤维网,合适的话趁冷预先压紧,以及于20-40巴的压力下压制,得到板或模制品。
在OSB生产中,将木刨花(线材)干燥至湿气水平为1-4%,分离为中间层材料和外层材料,在连续混合器中将粘合剂分开施用于这些材料。微胶囊可以以水溶液与粘合剂一起或与粘合剂分开在连续混合器中的干燥器上游添加到木刨花中,或者在施用粘合剂的过程中添加。还可以使用前述两种方法的组合。
为了制造板,于是由尚未粘结的涂覆有粘合剂的木刨花形成毡,合适的话趁冷预先压紧这些毡,然后于170-240℃的温度下在加热的压机中压制,得到板。
也可以将其它天然纤维材料如剑麻、黄麻、大麻、稻草、亚麻、椰子纤维、橡胶纤维以及其它天然纤维与粘合剂一起加工,得到板或模制品。天然纤维材料也可以以与合成纤维如聚丙烯、聚乙烯、聚酯、聚酰胺或聚丙烯腈的混合物使用。这些合成纤维也可以在这里与粘合剂组合物一起用作,用作共粘合剂。这里,合成纤维的比例优选小于50重量%,尤其小于30重量%,非常特别优选小于10重量%,基于所有的刨花、碎屑或纤维。纤维可以通过为木纤维板实施的方法加工。然而,也可以将预先形成的天然纤维毡用粘合剂组合物浸渍,合适的话还添加润湿助剂。然后,将经浸渍的毡——因粘合剂而是潮湿的或者经预先干燥——于100-250℃的温度和10-100巴的压力下压制,得到板或模制品。
还优选的是其中至少一个外层是基于熟石膏的模制模制品的复合元件。模制品优选是如WO 03016650中所述的纸面石膏板。为此,将呈粉末形式或分散体形式的微胶囊与熟石膏一起加工。这里,微胶囊的引入量优选为5-40重量%,尤其为20-35重量%,基于纸面石膏板的总重量(干重)。
纸面石膏板通常由石膏芯和施用于两侧上的纸板片材构成。它经常通过将熟石膏含水浆体分批或连续地引入到纤维素基纸板的两个片材中,由此形成板。石膏浆体如熟知的那样通过在含添加剂的水中连续添加并连续混合硫酸钙β-半水合物而制备。微胶囊可以与硫酸钙一起计量加入,或者使它们呈预先制备的水分散体形式。将所得熟石膏浆体施用于纸板片材,例如通过喷雾,并用纸板覆盖。
在初始的硬化过程中,将板在压机中模压,得到例如宽度为1.2-1.25m和厚度为9.25、12.5、15.0、18.0或25mm的带材。这些带材在几分钟内硬化,然后切成板。在该阶段,板通常仍旧包含为其重量的三分之一的尚未结合的水。为了除去残余水,将板于约250℃温度下进行热处理。所得纸面石膏板的密度为750-950kg/m3。
经常用于纸面石膏板的纸板的重量为约300g/m2。这类纸板通常制造成两层或更多层,最后一层为纸板的外层并且其重量为10-100g/m2,优选30-70g/m2。
还可以使用供选择的纤维状结构体代替纤维素基纸板作为本发明纸面石膏板的两个侧面的覆盖层。供选择的材料是由例如聚丙烯、聚酯、聚酰胺、聚丙烯酸酯、聚丙烯腈等组成的聚合物纤维。玻璃纤维也是合适的。供选择的材料的使用形式可以是织物形式,或者所谓的“无纺布”形式,即网状结构体。
这类纸面石膏板例如公开于US 4,810,569、US 4,195,110和US 4,394,411中。
对基材如纸板的增加粘合可以通过添加天然和/或合成聚合物来实现。合适的水溶性聚合物是:淀粉和淀粉醚,较高分子量的甲基纤维素和其它纤维素衍生物,瓜尔胶衍生物,热塑性分散粉末,以及基于乙酸乙烯酯、乙烯-乙酸乙烯酯、丙酸乙烯酯、苯乙烯-丁二烯、苯乙烯-丙烯酸酯和直链丙烯酸酯的液体分散体。聚合物的添加量基于熟石膏和潜热蓄积体的总干重为0.1-5重量%。
可以有利地添加到熟石膏组合物中的其它添加剂是保水剂和/或增稠剂。实例是聚乙烯醇,纤维素衍生物如羟乙基纤维素、羟丙基纤维素、羧甲基纤维素,聚丙烯酸,以及与丙烯酸的共聚物,如乙烯/丙烯酸共聚物、马来酸/丙烯酸共聚物、异丁烯/丙烯酸共聚物,以及含有苯乙烯或含丙烯酸酯或乙酸乙烯酯的富含丙烯酸的聚合物分散体,这些化合物用作增稠剂用于例如纸张整理。保水剂和/或增稠剂的通常用量基于熟石膏和潜热蓄积体的总干重为0.05-2重量%。
用于由硬质聚氨酯泡沫构成的复合元件的硬质泡沫已经已知很长时间了,并且广泛描述于文献中。它们通常通过有机多异氰酸酯与具有至少两个对异氰酸酯基具有反应性的氢原子的化合物(大多数多元醇)的反应来生产。
可以优选使用的有机多异氰酸酯c)是芳族多官能异氰酸酯。可以提及的具体实例是甲苯2,4-和2,6-二异氰酸酯(TDI)及相应的异构体混合物,二苯基甲烷4,4’、2,4’-和2,2’-二异氰酸酯(MDI)及相应的异构体混合物,由二苯基甲烷4,4’-和2,4’-二异氰酸酯组成的混合物,聚苯基聚甲基多异氰酸酯,二苯基甲烷4,4’-、2,4’-和2,2’-二异氰酸酯及聚苯基聚甲基多异氰酸酯的混合物(粗MDI),以及由粗MDI和甲苯二异氰酸酯组成的混合物。可以单独或以混合物形式使用有机二-和多异氰酸酯。
还经常使用所谓的改性多官能异氰酸酯,即通过有机二-和/或多异氰酸酯的化学反应获得的产物。可以提及的实例是包含异氰脲酸酯基团和/或包含氨基甲酸酯基团的二-和/或多异氰酸酯。改性多异氰酸酯合适的话可以相互混合,或者与未改性的有机多异氰酸酯如二苯基甲烷2,4’-或4,4’-二异氰酸酯、粗MDI或甲苯2,4-和/或2,6-二异氰酸酯混合。
除了这些,还可以使用多官能异氰酸酯与多官能多元醇或者它们与其它二-和多异氰酸酯的混合物的反应产物。
已证实特别成功的有机多异氰酸酯是NCO含量为29-33重量%且于25℃下的粘度为150-1000mpa.s的粗MDI。
具有至少两个对异氰酸酯基具有反应性的氢原子的特别化合物d)是OH数为100-1200mg KOH/g的聚醚醇和/或聚酯醇。
聚酯醇主要通过具有2-12个碳原子、优选2-6个碳原子的多元醇、优选二元醇与具有2-12个碳原子的多元羧酸例如琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、十二烷二甲酸、马来酸、富马酸或者优选的邻苯二甲酸、间苯二甲酸、对苯二甲酸或者萘二甲酸异构体的缩合而制备。
聚醚醇大部分具有的官能度为2-8,尤其3-8。特别是使用通过已知方法、例如通过氧化烯在催化剂、优选碱金属氢氧化物存在下的阴离子聚合制备的聚醚醇。
所用氧化烯主要是氧化乙烯和/或氧化丙烯,优选纯的1,2-氧化丙烯。
可以使用的起始分子尤其是分子中具有至少3个、优选4-8个羟基或者具有至少两个伯氨基的化合物。
可以优选使用的并且分子中具有至少3个、优选4-8个羟基的起始分子是三羟甲基丙烷、甘油、季戊四醇,糖化合物,如葡萄糖、山梨糖醇、甘露糖醇和蔗糖,多元酚,可溶性酚醛树脂,如苯酚与甲醛的低聚缩合物,以及由酚类、甲醛和二链烷醇胺构成的Mannich缩合物,以及还有蜜胺。
可以优选使用的并且分子中具有至少两个伯氨基的起始分子是芳族二-和/或多胺,如苯二胺,2,3-、2,4-、3,4-和2,6-甲苯二胺,以及4,4’-、2,4’-、和2,2’-二氨基二苯基甲烷,或者脂族二-和多胺,如乙二胺。
聚醚多元醇具有的官能度优选为3-8,并且羟基数优选为100-1200mgKOH/g,尤其240-570mg KOH/g。
在具有至少两个对异氰酸酯基具有反应性的氢原子的化合物d)中,还有合适的话皆伴随使用的交联剂和扩链剂。添加二官能的扩链剂、三官能或更高官能度的交联剂或者合适的话,这些化合物的混合物对于改性机械性能可能是有利的。优选使用的扩链剂和/或交联剂是链烷醇胺,尤其是分子量低于400、优选为60-300的二醇和/或三醇。
扩链剂、交联剂或它们的混合物的有利用量基于多元醇组分b)为1-20重量%,优选2-5重量%。
涉及使用的聚酯醇和聚醚醇以及它们的制备的进一步信息例如可见于Kunststoffhandbuch[塑料手册],第7卷,″聚氨酯″,Giinter Oertel编辑,Carl-Hanser-Verlag Munich,第3版,1993。
还可以使用聚氨酯化学常用的阻燃剂,如DE-A-101 24 333中所述的物质。
硬质聚氨酯泡沫经常在发泡剂、催化剂和泡孔稳定剂以及必要的话,其它助剂和/或添加剂存在下生产,这些物质在聚氨酯化学中是熟知的,并且描述于DE-A-101 24 333中,该文献特地引入此处作为参考。为此目的可以使用的助剂和/或添加剂是本身已知的物质,如表面活性剂,泡沫稳定剂,泡孔调节剂,填料,颜料,染料,阻燃剂,水解稳定剂,抗静电剂,抗真菌剂和抗细菌剂。涉及就所用起始原料、发泡剂、催化剂和助剂和/或添加剂而言的进行本发明方法的进一步信息可例如见于Kunststoffhandbuch,第7卷,″聚氨酯″,Carl-Hanser-Verlag Munich,第1版,1966和第2版,1983和第3版,1993。
硬质聚氨酯泡沫可以用于连续或分批生产用于户外的夹层元件,该元件的结构特征在于,它在一侧上具有常规的外层,而在对侧上具有根据本发明通过使用潜热蓄积材料改性的外层。
也可以连续或分批地生产用于户内的夹层元件,其中该元件的结构特征在于,在两侧上都具有根据本发明通过使用潜热蓄积材料改性的外层。
硬质聚氨酯泡沫可以借助已知的混合装置来分批或连续生产。本发明复合元件优选由硬质泡沫在连续操作的双传送带系统上生产。这里,使用高压机器进料多元醇组分和异氰酸酯组分,这两个组分在混合头中混合。可以提前将催化剂和/或发泡剂通过分开的泵计量加入多元醇混合物中。起始组分主要在15-35℃、优选20-30℃的温度下混合。将反应混合物连续施用于下面的外层。使带有反应混合物的下面的外层和上面的外层运行到双传送带系统中,在其中反应混合物发泡并固化。一旦连续的带材已经离开双传送带系统,将其切成所需尺寸。该方法还可以生产具有相同或不同外层的本发明复合元件,这称之为夹层元件。本发明复合元件的厚度经常为20-300mm,用于生产这些模制品的硬质聚氨酯泡沫的通常密度范围为10-60kg/m3,优选30-50kg/m3(Kunststoffhandbuch[塑料手册],第3版,第150页)。
还可以使用高压或低压进料机将反应混合物注入关闭的支持性模具(例如压模)。该技术用于例如分批制造本发明的复合元件。
复合元件可以消除令人不满意的内部大气条件。由该元件生产的建筑物显示出不仅良好的隔热性,而且还显示出就温度分布而言并因此在能量消耗方面的显著改进。
下列实施例意欲更详细描述本发明。
实施例1
生产夹层元件,该元件由厚度为0.6mm的仿形钢外层(朝外侧)、Elastopor硬质聚氨酯泡沫体系(Elastogran,多元醇组分A与异氰酸酯组分B的混合比=100∶106)和用潜热蓄积体改性的熟石膏板(厚度15mm,玻璃纤维增强,包含30重量%微胶囊化潜热蓄积材料=3kg PCM/m2,朝内侧)构成。该模制品的尺寸为2000×1150×100mm。泡沫体的封包芯密度为36.4kg/m3,其导热率为约23mW/mK。含熟石膏的朝内层在熔点区域中的热容为330kJ/m2。本发明夹层元件的导热率因此与常规夹层元件的导热率相同(金属/PU/金属),然而,本发明夹层元件的热容330kJ/m2明显高于常规夹层元件的热容0.67kJ/m2。(钢层的比热容为0.48kJ/kgK。温度范围认为是3K。)
实施例2
也按照实施例1生产由仿形钢外层、上述钢性聚氨酯泡沫体系和常规的刨花板(厚19mm)构成的夹层元件。该模制品的尺寸为2700×1170×120mm。这表明,这类材料组合物原则上是可行的。
本发明夹层元件可以类似地用含PCM的刨花板生产。
这些实验显示,可以生产直接兼备高蓄热能力和高隔热性能的夹层元件。
Claims (11)
1.一种由硬质聚氨酯泡沫和两个外层构成的复合元件,其中至少一个外层是用微胶囊改性的模制品,并且该微胶囊包含聚合物作为胶囊壁和主要由潜热蓄积材料组成的胶囊芯。
2.根据权利要求1的复合元件,其中至少一个外层是由含木素纤维素的材料组成的改性模制品。
3.根据权利要求1的复合元件,其中至少一个外层是基于熟石膏的改性模制品。
4.根据权利要求1-3中任一项的复合元件,其中潜热蓄积材料是在-20至120℃的温度范围内具有固/液相转变的亲脂性物质。
5.根据权利要求1-4中任一项的复合元件,其中潜热蓄积材料是脂族烃化合物。
6.根据权利要求1-5中任一项的复合元件,其中胶囊壁是高度交联的甲基丙烯酸酯聚合物。
7.根据权利要求1-6中任一项的复合元件,其中胶囊壁由下列组分组成:
30-100重量%的一种或多种丙烯酸和/或甲基丙烯酸的C1-C24烷基酯(单体I),
0-80重量%的不溶于或微溶于水的双-或多官能单体(单体II),以及
0-40重量%其它单体(单体III),在每种情况下都基于单体的总重量。
8.根据权利要求1-7中任一项的复合元件,其中微胶囊可通过加热包含单体、自由基引发剂和作为分散相的潜热蓄积材料的水包油乳液而获得。
9.根据权利要求1、2和4-8中任一项的复合元件,其中模制品包含含木素纤维素的材料和选自氨基塑料树脂、酚类树脂、异氰酸酯树脂和聚羧酸树脂的粘合剂树脂。
10.根据权利要求9的复合元件,其中粘合剂树脂是尿素-和/或蜜胺-甲醛树脂。
11.根据权利要求1、2和4-10中任一项的复合元件,其中模制品包含含木素纤维素的材料以及基于模制品的重量为:
5-20重量%的按固体计的粘合剂树脂,和
2-30重量%的具有聚合物作为胶囊壁和胶囊芯主要由潜热蓄积材料组成的微胶囊。
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DE102004041298A DE102004041298A1 (de) | 2004-08-25 | 2004-08-25 | Verbundelemente aus Polyurethan-Hartschaumstoff |
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EP (1) | EP1784546B1 (zh) |
JP (1) | JP2008510905A (zh) |
KR (1) | KR20070046949A (zh) |
CN (1) | CN101006233A (zh) |
AT (1) | ATE509170T1 (zh) |
BR (1) | BRPI0514618A (zh) |
DE (1) | DE102004041298A1 (zh) |
ES (1) | ES2366568T3 (zh) |
MX (1) | MX2007001870A (zh) |
PL (1) | PL1784546T3 (zh) |
WO (1) | WO2006021306A1 (zh) |
Cited By (2)
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CN102317073A (zh) * | 2008-12-17 | 2012-01-11 | 巴斯夫欧洲公司 | 由复合材料制成的层状建筑部件 |
CN102470067A (zh) * | 2009-08-26 | 2012-05-23 | 拜尔材料科学股份公司 | 具有潜热储存单元的聚氨酯泡沫材料 |
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DE202007012999U1 (de) * | 2007-09-17 | 2008-03-27 | Ilkazell Isoliertechnik Gmbh Zwickau | Vorgefertigtes Verbundplattenelement zum Klimatisieren von Räumen |
DE102008031163A1 (de) | 2008-07-03 | 2010-01-07 | Bayerisches Zentrum für Angewandte Energieforschung e.V. | Mit Latentwärmespeichermaterial (PCM) gefüllte Hohlfaser, Verfahren zu deren Herstellung sowie Verwendung dieser |
FR2937064B1 (fr) * | 2008-10-10 | 2012-11-16 | Arcelormittal France | Panneau composite pour paroi et procede de fabrication. |
WO2011159379A1 (en) * | 2010-06-18 | 2011-12-22 | Georgia-Pacific Gypsum Llc | Building material containing latent heat storage material and methods of making the same |
DE102011079299A1 (de) | 2010-07-20 | 2012-01-26 | Basf Se | Verbundmaterials enthaltend Latentwärmespeicher |
DE102010036120B4 (de) * | 2010-09-01 | 2013-11-21 | Nora Systems Gmbh | Bodenbelag |
WO2012142322A2 (en) * | 2011-04-12 | 2012-10-18 | ATI Industries, Inc. | Light weight composite structural support material having natural oil and polyol foam bonded directly between substrates |
RU2471627C2 (ru) * | 2011-04-15 | 2013-01-10 | Олег Савельевич Кочетов | Установка для получения пенопласта из пенообразующей и смоляной композиции |
RU2014135488A (ru) * | 2012-02-02 | 2016-03-20 | Байер Интеллектуэль Проперти Гмбх | Способ непрерывного изготовления композитных сэндвич-элементов |
US20150040503A1 (en) * | 2013-08-09 | 2015-02-12 | Firestone Building Products Co, Llc | Roofing system and method for preparing the same |
KR101624334B1 (ko) | 2014-03-26 | 2016-05-25 | 황창연 | 단열재 보호필름 및 그 제조방법 |
US11149446B2 (en) | 2018-09-10 | 2021-10-19 | Champion Link International Corporation | Floor panel comprising a ceramic material or a natural stone |
CN115302593A (zh) * | 2022-07-06 | 2022-11-08 | 浙江华丽家具有限公司 | 一种低甲醛生态板及其生产工艺 |
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US3062699A (en) * | 1960-06-28 | 1962-11-06 | Spaulding Fibre Company Inc | Process for modifying cellulosic materials and product thereof |
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DE19638686A1 (de) * | 1996-09-20 | 1998-03-26 | Basf Ag | Wäßrige Dispersion eines biologisch abbaubaren Polyesters sowie deren Verwendung |
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2004
- 2004-08-25 DE DE102004041298A patent/DE102004041298A1/de not_active Withdrawn
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2005
- 2005-08-04 AT AT05768557T patent/ATE509170T1/de active
- 2005-08-04 PL PL05768557T patent/PL1784546T3/pl unknown
- 2005-08-04 EP EP20050768557 patent/EP1784546B1/de not_active Not-in-force
- 2005-08-04 ES ES05768557T patent/ES2366568T3/es active Active
- 2005-08-04 CN CNA200580028050XA patent/CN101006233A/zh active Pending
- 2005-08-04 JP JP2007528657A patent/JP2008510905A/ja active Pending
- 2005-08-04 US US11/573,356 patent/US7662469B2/en not_active Expired - Fee Related
- 2005-08-04 MX MX2007001870A patent/MX2007001870A/es not_active Application Discontinuation
- 2005-08-04 BR BRPI0514618-6A patent/BRPI0514618A/pt not_active IP Right Cessation
- 2005-08-04 WO PCT/EP2005/008442 patent/WO2006021306A1/de active Application Filing
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102317073A (zh) * | 2008-12-17 | 2012-01-11 | 巴斯夫欧洲公司 | 由复合材料制成的层状建筑部件 |
CN102317073B (zh) * | 2008-12-17 | 2014-07-16 | 巴斯夫欧洲公司 | 由复合材料制成的层状建筑部件 |
CN102470067A (zh) * | 2009-08-26 | 2012-05-23 | 拜尔材料科学股份公司 | 具有潜热储存单元的聚氨酯泡沫材料 |
Also Published As
Publication number | Publication date |
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BRPI0514618A (pt) | 2008-06-17 |
KR20070046949A (ko) | 2007-05-03 |
JP2008510905A (ja) | 2008-04-10 |
EP1784546B1 (de) | 2011-05-11 |
EP1784546A1 (de) | 2007-05-16 |
PL1784546T3 (pl) | 2011-10-31 |
ATE509170T1 (de) | 2011-05-15 |
US20080014411A1 (en) | 2008-01-17 |
DE102004041298A1 (de) | 2006-03-02 |
ES2366568T3 (es) | 2011-10-21 |
US7662469B2 (en) | 2010-02-16 |
WO2006021306A1 (de) | 2006-03-02 |
MX2007001870A (es) | 2007-04-24 |
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