CN103547617B - 包含中空微球的三聚氰胺-甲醛泡沫 - Google Patents
包含中空微球的三聚氰胺-甲醛泡沫 Download PDFInfo
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- CN103547617B CN103547617B CN201280024036.2A CN201280024036A CN103547617B CN 103547617 B CN103547617 B CN 103547617B CN 201280024036 A CN201280024036 A CN 201280024036A CN 103547617 B CN103547617 B CN 103547617B
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- melamine
- foam
- hollow microsphere
- formaldehyde
- weight
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Classifications
-
- 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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
-
- 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
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- 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
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Abstract
本发明涉及包含中空微球的三聚氰胺-甲醛泡沫,其中所述中空微球的中值粒径(D50,体积平均,Malvern,夫琅禾费衍射)范围为260μm至490μm,并且还涉及所述三聚氰胺-甲醛泡沫的制备方法及其用途。
Description
本发明涉及包含中空微球的三聚氰胺-甲醛泡沫。
EP-A-17672和EP-37470已经公开了基于三聚氰胺-甲醛的缩合产物的泡沫及其制备方法。
使此类泡沫具有中空微球也是已知的。所述中空微球可以包含活性物质或有效物质,例如作为潜热储能介质并因此改善三聚氰胺-甲醛泡沫绝热特性的物质,或者香味剂或生物杀灭活性物质,其在中空微球壁受到破坏时释放出来,从而发挥其用于特定所需目的的特定作用。还可类似地通过封装并随后释放疏水性物质例如硅油而使泡沫结构疏水化。
欧洲专利申请EP10152499.9(文件号)记载了例如包含中值粒径为0.5-100μm的微球的三聚氰胺-甲醛泡沫。这些微球优选被纳入至泡沫结构的结点或支柱(strut)。
欧洲专利申请EP09176634.5(文件号)记载了包含中值粒径为70-250μm的发泡中空微球的三聚氰胺-甲醛泡沫。所述中空微球优选地纳入至泡沫结构的孔中。纳入至孔中通过多步制备方法实现,其中,在第一步中制备三聚氰胺-甲醛泡沫,在第二步额外的浸渍步骤中将中空微球引入泡沫。
然而,特别是在使用中空微球的高载量下,纳入至泡沫结构的结点或支柱可能伴随有对发泡操作和/或泡沫机械特性的损害。随后对泡沫的浸渍为额外的必要加工步骤,并且,另一方面,随着载量增加,难以将中空微球引入并固定于泡沫。
因此,本发明解决的问题是提供一种具有中空微球的三聚氰胺-甲醛泡沫,所述泡沫即使在高载量(即中空微球的含量和任何相关活性物质和有效物质的含量)下也可基本上保持良好的机械泡沫特性,使中空微球在泡沫中的固定性更好,并且可以以简单的方法获得而不需要额外的制备步骤。
我们已经发现,所述问题通过含有中空微球的新型三聚氰胺-甲醛泡沫而解决,其中所述中空微球的中值粒径(D50,体积平均,Malvern,夫琅禾费(Fraunhofer)衍射)范围为260μm至490μm。还发现了这些三聚氰胺-甲醛泡沫的制备方法及其用途。
本发明的三聚氰胺-甲醛泡沫特别是在高载量(即中空微球的含量和任何相关活性物质和有效物质的含量)下具有良好的机械泡沫特性以及中空微球在泡沫中更好的固定性。此外,中空微球可在泡沫制备过程中被纳入泡沫中,而不需要额外的加工步骤。
下文将描述本发明的制品、方法和用途。
三聚氰胺-甲醛泡沫本身及其制备以及中空微球本身及其制备是本领域技术人员已知的并且记载于文献中(参见例如开篇提及的参考文献)。
本发明的三聚氰胺-甲醛泡沫包含中空微球,并且,按照基本要求,这些中空微球的中值粒径(D50,体积平均,Malvern,夫琅禾费衍射)范围为260μm至490μm,优选范围为280μm至450μm,且更优选范围为300μm至400μm。
中空微球的含量范围通常为0.1重量%至60重量%,优选范围为5重量%至50重量%,且更优选范围为10重量%至30重量%,所述重量均基于用于制备泡沫的中空微球和三聚氰胺-甲醛预缩合物的总重量计。
三聚氰胺-甲醛泡沫具有包含多重互相连接的三维枝型支柱(branched strut)(支柱之间的连接点被称为“结”或“结点”)的开孔泡沫支架。对本发明和下文所述的本发明三聚氰胺-甲醛泡沫的制备方法而言重要的中空微球的中值粒径使得中空微球优先嵌入泡沫结构的开孔中。如果纳入,则向泡沫支架的支柱或结点内的纳入进行得并不明显。因此,即使在高中空微球含量下,也可实现中空微球在泡沫中良好的固定,而不会过度影响泡沫的机械特性。
本发明包含中空微球的三聚氰胺-甲醛泡沫优选由连续的方法步骤a)和b)获得:
a)将含有三聚氰胺:甲醛的摩尔比范围为1:1.3至1:5并且优选范围为1:1.5至1:3.5的三聚氰胺-甲醛预缩合物、中空微球、固化剂、分散剂和发泡剂的混合物加热至发泡并交联,和
b)干燥步骤a)中得到的泡沫,
其中,这些方法步骤以及可用于步骤a)的三聚氰胺-甲醛预缩合物、固化剂、分散剂和发泡剂原则上是本领域技术人员已知的并且记载于文献中(参见例如开篇引用的参考文献)。
除三聚氰胺和甲醛外,三聚氰胺-甲醛预缩合物可以含有最高达50重量%且优选最高达20重量%(均基于共缩合三聚氰胺的重量计)的其它热固性成形成物和最高达50重量%且优选最高达20重量%(均基于共缩合甲醛的重量计)的共缩合形式的其它醛。可用的热固性形成物包括例如:烷基-取代的和芳基-烷基-取代的三聚氰胺、脲、氨基甲酸酯、羧酰胺、双氰胺、胍、磺酰胺(sulfurylamide)、磺酰胺(sulfonamide)、脂族胺、二元醇、苯酚及其衍生物。可用的其它醛的实例为乙醛、三羟甲基乙醛、丙烯醛、苯甲醛、糠醛、乙二醛、戊二醛、邻苯二甲醛(phthalaldehyde)和对苯二甲醛。特别优选为未改性的三聚氰胺-甲醛预缩合物,即不含任何其它热固性形成物或其它醛的三聚氰胺-甲醛预缩合物。关于三聚氰胺-甲醛缩合产物的进一步细节可见于Houben-Weyl,Methoden der organischen Chemie,第14/2卷,1963,第319至402页。
市售可得的三聚氰胺-甲醛预缩合物可以用于多种应用领域,例如进一步加工为胶。含有亚硫酸酯基团的三聚氰胺甲醛预缩合物对于用于某些所述领域是有利的。所述含有亚硫酸酯基团的三聚氰胺甲醛预缩合物可由例如EP–B37470所记载的方法得到,其中在三聚氰胺和甲醛缩合的过程中加入1重量%至20重量%的亚硫酸氢钠,以获得共缩合的亚硫酸酯基团。然而,对于本发明方法而言,有利的是步骤a)使用不含亚硫酸酯基团的预缩合物。
步骤a)中发泡剂的乳化和泡沫的稳定需要加入分散剂,例如乳化剂或乳化剂混合物。可用的乳化剂包括阴离子表面活性剂、阳离子表面活性剂和非离子表面活性剂及其混合物。
合适的阴离子表面活性剂为二苯醚磺酸盐、烷烃磺酸盐和烷基苯磺酸盐、烷基萘磺酸盐、烯烃磺酸盐、烷基醚磺酸盐、脂肪醇硫酸盐、醚硫酸盐、α-磺基脂肪酸酯、酰基氨基烷烃磺酸盐、酰基羟乙基磺酸盐、烷基醚羧酸盐、N-酰基肌氨酸盐、烷基磷酸盐和烷基醚磷酸盐。可用的非离子表面活性剂包括烷基酚聚乙二醇醚、脂肪醇聚乙二醇醚、脂肪酸聚乙二醇醚、脂肪酸烷醇酰胺、EO-PO嵌段共聚物、胺氧化物、甘油脂肪酸酯、山梨醇酯和烷基多糖苷。可用的阳离子乳化剂包括烷基三铵盐、烷基苄基二甲基铵盐和烷基吡啶盐。乳化剂优选以0.2重量%至5重量%的量加入,基于三聚氰胺-甲醛预缩合物计。
对于三聚氰胺-甲醛预缩合物——其优选地以水溶液或分散体的形式使用以制备步骤a)中的泡沫——而言,其必须包含发泡剂,所述发泡剂的含量取决于所需的泡沫密度。原则上,本发明的方法既可以使用物理发泡剂也可以使用化学发泡剂。可用的物理发泡剂包括,例如液体形式的烃、卤代烃且更特别是氟代烃、醇、醚、酮和酯或作为气体的空气和CO2。可用的化学发泡剂包括,例如与水混合的异氰酸酯,在该情况下释放出CO2作为有效的发泡剂,此外,与酸混合的碳酸盐和碳酸氢盐同样产生CO2,以及偶氮化合物,例如偶氮二甲酰胺。在本发明一个的优选实施方案中,将三聚氰胺-甲醛预缩合物的水溶液或分散体与1重量%至40重量%的沸点为0至80℃的物理发泡剂混合,基于三聚氰胺-甲醛预缩合物计;在戊烷的情况下,所用的量优选范围为5重量%至15重量%。
步骤a)中使用的固化剂包括催化三聚氰胺-甲醛预缩合物进一步缩合的酸性化合物。用量为0.01重量%至20重量%,优选0.05重量%至5重量%,基于三聚氰胺-甲醛预缩合物计。可以使用无机酸和有机酸,实例为盐酸、硫酸、磷酸、硝酸、甲酸、乙酸、草酸、甲苯磺酸、酰胺基磺酸及酸酐。
步骤a)中使用的三聚氰胺-甲醛预缩合物的水溶液和分散体优选不含其它加入的物质。但是,为了某些目的,有利的是加入最高达20重量%、优选小于10重量%的常规添加物如染料、阻燃剂、UV稳定剂、降低可燃气体毒性或促进碳化的试剂,基于三聚氰胺-甲醛预缩合物计。由于泡沫通常为开孔的并能够吸水,某些应用使得有必要加入用量为0.2重量%至5重量%的疏水剂。可用的疏水剂包括例如硅酮、石蜡、硅酮表面活性剂、氟表面活性剂、疏水含烃表面活性剂、硅酮乳化剂和氟碳乳化剂。
预缩合物与溶剂/分散剂(更具体而言是水)的混合物中三聚氰胺-甲醛预缩合物的浓度可以在55重量%至85重量%并且优选63重量%至80重量%的宽范围内变化,均基于三聚氰胺-甲醛预缩合物和溶剂/分散剂的总重量计。预缩合物与溶剂/分散剂混合物的优选粘度为1至3000dPa.s,且优选为5-2000dPa.s。
将中空微球和其它混合物组分与三聚氰胺-甲醛预缩合物的水溶液或分散体混合以形成均匀的混合物,如有必要在加压下压入发泡剂。然而,还可以由固体例如喷雾干燥的三聚氰胺-甲醛预缩合物起始,并且随后将其与中空微球的分散体和/或与乳化剂的水溶液、与固化剂以及与发泡剂混合。混合后,经加热的具有分散的发泡剂的树脂混合物通过模头排出,然后发泡。
含发泡剂的溶液或分散体的发泡从模头一出来即通过热气或高频辐射开始变大,如EP–B17671中记载的。优选地,可通过电磁辐射输入能量,例如通过在在频率范围为0.2至100GHz、优选0.5至10GHz下使用的每千克混合物用5至400kW,优选5至200kW并且特别优选9至120kW的高频辐射下输入。磁控管为合适的电介质辐射的辐射源,能够同时用一个或多个磁控管辐照。
待发泡的混合物一从发泡模头出来即对其进行辐照。发泡剂蒸发,树脂混合物发泡并同时固化。
最后,干燥制得的泡沫以移除泡沫中剩余的水和发泡剂。
在本发明的另一实施方案中,在方法步骤b)后可进行方法步骤c),其中将经干燥的泡沫压制成型以使其具有弹性。
方法步骤c)原则上是本领域技术人员已知的并记载于文献例如EP-A1505105和EP-B37470中。
所获得的泡沫块或泡沫片任选地可以在进一步的方法步骤中进行热压。热压本身是本领域技术人员已知的并记载于例如WO2007/031944、EP-A451535、EP-A111860和US-B6,608,118中。热压通常可以使中空微球在泡沫结构中具有更好的固定性。
用于制备本发明三聚氰胺-甲醛泡沫的优选的中空微球具有由聚合物、无机材料或无机材料与聚合物的结合(例如通过粘附无机材料)组成的壁。
适合于中空微球壁的聚合物优选为聚氨酯、三聚氰胺-甲醛树脂、环氧树脂、聚酯、聚碳酸酯、聚丙烯酸酯、聚酰胺或其混合物。
用作中空微球壁的无机材料优选为硅酸盐,特别是铝、钙、镁和/或锆的硅酸盐;氧化物如氧化铝、石英、菱镁矿、多铝红柱石、铬铁矿、氧化锆和/或氧化钛;硼化物、碳化物和氮化物如碳化硅、碳化钛、硼化钛、氮化硼和/或碳化硼;碳或玻璃并且更优选玻璃。
中空微球的内部可含有气体例如空气,或者可以被抽成真空。优选地,中空微球的内部至少部分并且更特别是全部填充有一种或多种固态或液态活性物质或有效物质。活性物质或有效物质为例如作为潜热储能介质并因此能够改善三聚氰胺-甲醛泡沫绝热特性的物质,或表面活性剂、洗涤剂或染料,例如油墨、香味剂或生物杀灭活性物质,其通过中空微球壁的破坏而释放,从而发挥其用于特定所需用途的特定作用。本身为本领域技术人员已知的其它可用的活性物质或有效物质为例如疏水化试剂;影响触觉或土壤释放性能(例如为了获得所谓的莲花效应(lotus effect))的物质;降低烟气毒性的物质;甲醛清除剂;膨胀剂;磨料,例如无机纳米颗粒(参见例如WO2009/021963);或催化剂。
优选的包含基于高度交联甲基丙烯酸酯聚合物的壁材料的中空微球已知于EP-A-1029018、DE-A-10139171和WO-A-2005/116559中。其均涉及不同领域使用的微胶囊化的潜热储能材料。EP-A-1029018教导了在粘合的建筑物材料例如混凝土和石膏中的用途,DE-A-10139171教导了微胶囊化的潜热储能材料在石膏板中的用途,且WO-A-2005/116559教导了其在硬纸板中的用途。记载于这些参考文献中的中空微球据称均在热处理中、化学处理中以及在压力下具有高防渗性。
中空微球可通过例如所谓的原位聚合而获得。中空微球形成的原理基础为使待封装的单体、自由基引发剂、保护胶体和亲油性物质结合以形成稳定的水包油乳液。然后,单体的聚合通过加热引发,并任选地通过进一步升温而控制,得到的聚合物形成封闭有亲油性物质的中空球壁。该一般原理记载于例如DE-A-102007055813、WO2008071649和DE-A-10139171中,其内容在此特别以引用的方式纳入本文。
DE-A-102007055813记载了可热损坏的中空微球的制备和用途,其同样为优选的。所述中空微球壁由丙烯酸酯构成。所述中空微球的内部含有亲油性物质,如脂族烃和芳族烃化合物、饱和或不饱和C6-C30脂肪酸、脂肪醇、C5-C30脂肪胺、脂肪酸酯、天然蜡或合成蜡、卤代烃、硅油、粘合剂、芳香化学品、香味剂、活性物质、染料、成色剂、颜料和交联剂。
中空微球内部与中空微球壁的重量比,即芯/壁比范围通常为50:50至95:5,优选范围为70:30至95:5,且更优选范围为75:25至93:7。
本发明获得的三聚氰胺-甲醛泡沫的密度范围通常为3-100g/l,且更优选范围为5-50g/l。
本发明包含中空微球的三聚氰胺-甲醛泡沫可以间歇的方式获得或优选作为片材或网状物而连续获得,所述片材或网状物通常为任何需要的厚度,有利的层厚范围为0.1-500cm,优选0.5-200cm,更优选1-100cm,更特别地为3-80cm,且最优选为5-50cm。包含本发明三聚氰胺-甲醛泡沫的模塑物可以连续的方式并且优选以间歇的方式获得。
网状物、片材、模塑物形式或某种其它形式的三聚氰胺-甲醛泡沫可以通过常规的方法将表面层层压或给予至一面、两面、更多面或所有面,例如用纸、纸板、玻璃覆面毡片(glass overlay matt)、木材、石膏板、金属片材或金属箔、塑料或自支撑塑料泡沫/片材——其也可任选地为发泡的——层压或给予。表层可以在发泡过程中施用或随后施用。在随后施用的情况下,使用粘合促进剂是有利的。
当本发明的三聚氰胺-甲醛泡沫包含填充有待释放的活性物质或有效物质的中空微球时,所述释放可以在任何需要的时间通过对泡沫施用合适的机械作用或热作用而进行。例如,上述活性物质或有效物质(例如表面活性剂、洗涤剂或染料如油墨、香味剂或生物杀灭作用物质)可通过对中空微球壁的热破坏(例如热空气、各种形式的辐射例如红外辐射或微波辐射)或机械破坏(压、辊压、超声等)而释放。这均匀或几乎均匀地释放中空微球的内容物,并使表面结构(支柱和结点)润湿,即使在开孔三聚氰胺-甲醛泡沫结构的内部也被润湿。对微胶囊壁进行热破坏或机械破坏的方法原则上是本领域技术人员已知的并记载于文献中。例如,泡沫可以被压缩成型以破坏微胶囊壁,例如EP-A0451535中所记载的,通过将泡沫导入平行排列的两个反向旋转辊之间的限定的间隙中进行。除了将泡沫导入两个共旋转辊之间的间隙以外,还可以在传送带上传送泡沫,并且可使轧辊向下压泡沫,所述轧辊以与泡沫移动速度相同的圆周速度旋转。对泡沫的压力可以进一步通过例如将泡沫置于压机(其中有一个柱塞(ram)向下压缩泡沫)而施加。然而,在此情况下无法实现连续施压。
应当理解,中空微球还可含有即使不破坏微胶囊壁也能发挥其活性/作用的活性物质或有效物质;例如,阻燃物质仅在有火时才呈现出活性,并且即使在被封装的形式中也可发挥其活性/作用。
本发明的三聚氰胺-甲醛泡沫可用于建筑物、车辆、铁路、轮船和飞机结构及太空旅行中隔音或隔热,以及用作座椅区域衬垫的缓冲材料。
本发明的三聚氰胺-甲醛泡沫更特别是即使在高载量(即中空微球的含量和任选的相关活性物质或有效物质的含量)下也表现出良好的泡沫机械特性和中空微球在泡沫中更好的固定性。此外,所述中空微球可在泡沫制备过程中被纳入泡沫中而不需要额外的方法步骤。
通过以下实施例阐释本发明。
实施例
测量方法:
机械特性,弹性:
用于评价三聚氰胺树脂泡沫机械质量的柱塞压力测量均如US-A-4666948中所记载的进行。将直径8mm且高10cm的圆柱形柱塞沿发泡方向以90°角压入直径11cm且高5cm的圆柱形样品中直至样品撕裂。撕裂力[N](下文也被称为柱塞压力值)提供了泡沫质量的信息。
对比实施例V-1
制备不含中空微球的三聚氰胺-甲醛泡沫(根据WO-A-2009/021963):
将75重量份经喷雾干燥的三聚氰胺-甲醛预缩合物(摩尔比为1:3)溶于25重量份的水中,然后加入3重量%甲酸、2重量%C12/C14-烷基硫酸钠、38重量%戊烷,所有重量%均基于预缩合物的重量计,然后搅拌,并随后在聚丙烯模具(用于发泡)中通过用微波能量辐照而发泡。发泡后,将泡沫干燥30分钟。
该三聚氰胺-甲醛泡沫的密度为7.5g/l且柱塞压力值为18.9N。
本发明实施例4和比较实施例V-2、V-3和V-5:
在每种情况下,将75重量份经喷雾干燥的三聚氰胺-甲醛预缩合物(摩尔比三聚氰胺:甲醛为1:3)溶于25重量份的水中。将该混合物与3重量份甲酸、2重量份作为表面活性剂的脂肪醇聚乙二醇醚、38重量份戊烷和10重量%(基于三聚氰胺-甲醛预缩合物的总重量计)基于钠钙硅酸盐玻璃(soda-lime silicate glass)的中空玻璃微球混合,所述微球平均粒径(D50,体积平均,Malvern,夫琅禾费衍射)和体积密度述于表1。剧烈搅拌该混合物,随后在聚丙烯发泡模具中通过用2.54GHz的微波能量辐照而发泡。随后用热空气干燥每种情况下形成的泡沫。
每种情况下获得的三聚氰胺-甲醛泡沫的特性记录于表1。
表1:中空微球的含量和尺寸以及三聚氰胺-甲醛泡沫的特性
Claims (7)
1.一种包含中空微球的三聚氰胺-甲醛泡沫,其中,所述中空微球嵌入泡沫结构的开孔中并且其中值粒径范围为260μm至490μm,其中所述中值粒径是指体积平均直径D50,其根据Malvern,夫琅禾费衍射测量。
2.权利要求1的三聚氰胺-甲醛泡沫,其中,所述中空微球的含量范围为0.1重量%至60重量%,其中重量%基于用于制备泡沫的中空微球和三聚氰胺-甲醛预缩合物的总重量计。
3.权利要求1或2的三聚氰胺-甲醛泡沫,其中,所述中空微球壁由聚合物或无机材料组成。
4.权利要求1或2的三聚氰胺-甲醛泡沫,其中,所述中空微球壁由玻璃组成。
5.权利要求1或2的三聚氰胺-甲醛泡沫,其中,所述中空微球的内部至少部分填充有活性物质或有效物质。
6.制备权利要求1至5任一项的包含中空微球的三聚氰胺-甲醛泡沫的方法,其中,进行连续的方法步骤a)和b):
a)将含有三聚氰胺:甲醛摩尔比范围为1:1.3至1:5的三聚氰胺-甲醛预缩合物、中值粒径范围为260μm至490μm的中空微球、固化剂、分散剂和发泡剂的混合物加热以发泡并交联,和
b)干燥步骤a)中得到的泡沫;
其中所述中值粒径是指体积平均直径D50,其根据Malvern,夫琅禾费衍射测量。
7.权利要求1至5任一项的包含中空微球的三聚氰胺-甲醛泡沫作为缓冲材料和用于隔热、隔冷和隔音的用途。
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