CN101198646B - 可热成型的具有低甲醛散发量的蜜胺/甲醛泡沫 - Google Patents
可热成型的具有低甲醛散发量的蜜胺/甲醛泡沫 Download PDFInfo
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Abstract
本发明涉及一种通过使包含蜜胺/甲醛(MF)预缩合物、固化剂和发泡剂的混合物发泡并交联而加热生产泡沫的方法，其中在加热之前加入甲醛捕捉剂。还公开了基于蜜胺/甲醛泡沫的具有低甲醛散发量的可热成型泡沫及其在通过热成型生产成型制品中的用途。
Description
本发明涉及一种生产具有低甲醛散发量的基于蜜胺/甲醛树脂的泡沫的方法，以及在通过热成型生产成型制品中的用途。
基于蜜胺/甲醛树脂的开孔弹性泡沫，以及通过用热空气、蒸汽或微波辐照加热，并且使含有发泡剂的蜜胺/甲醛预缩合物的溶液或分散体发泡并交联的而生产它们方法是已知的且例如描述在EP-A 17672和EP-A 37470中。
基于甲醛树脂的泡沫散发少量甲醛。甲醛散发量随着温度和湿度的增加而增加。因此WO 01/94436描述了一种生产具有低甲醛散发量的基于蜜胺/甲醛缩合物的泡沫的方法，其中使用蜜胺与甲醛的摩尔比超过1∶2的MF预缩合物。为实现很低的甲醛散发量，必须在干燥之后在220℃下将泡沫再加热30分钟。然而，在加热之后泡沫已经固化并不再可热成型。
因此EP-A 1 505 105描述了一种由蜜胺/甲醛泡沫生产具有低甲醛散发量的成型制品的方法，其中在生产之后和热成型之前，在100-160℃的温度下加热泡沫。
本发明的目的为提供一种生产可热成型，同时甚至在热成型以产生成型制品之前具有低甲醛散发量的蜜胺/甲醛泡沫的方法。
因此，找到了一种通过使包含蜜胺/甲醛(MF)预缩合物、固化剂和发泡剂的混合物发泡并交联而加热生产泡沫的方法，其中在加热之前加入甲醛捕捉剂。
合适的甲醛捕捉剂例如为脲、取代的脲、烷基或芳基取代的蜜胺、尿烷、羧酰胺、双氰胺、胍、硫酰胺(sulfurylamide)、磺酰胺、脂族胺、二醇或酚类。甲醛捕捉剂基于蜜胺/甲醛(MF)预缩合物通常以2-20％，优选5-15％的量加入。在一个实施方案中，甲醛捕捉剂基于蜜胺/甲醛(MF)预缩合物以2-10重量％的量加入。
本发明方法起始于蜜胺/甲醛预缩合物。蜜胺/甲醛预缩合物可包含以缩合单元形式掺入的至多50重量％，优选至多20重量％的除了蜜胺之外的其它热固性塑料的前体，以及至多50重量％，优选至多20重量％的除了甲醛之外的其它醛。特别优选未改性的蜜胺/甲醛缩合物。合适的热固性塑料的母体的实例为：烷基和芳烷基取代的蜜胺、脲、尿烷、羧酰胺、双氰胺、胍、硫酰胺、磺酰胺、脂族胺、二醇、苯酚及其衍生物。可使用的醛例如为乙醛、三羟甲基乙醛、丙烯醛、苯甲醛、糠醛、乙二醛、戊二醛、邻苯二醛和对苯二醛。关于蜜胺/甲醛缩合物的其它细节可在Houben-Weyl，Methoden der organischen Chemie，第14/2卷，1963第319-402页中找到。
蜜胺与甲醛的摩尔比通常小于1∶1.0，优选1∶1.2-1∶4.0，尤其是1∶1.3-1∶1.8。根据EP-B 37470，有利的是蜜胺树脂包含以缩合单元形式掺入的亚硫酸盐基，其例如可通过在树脂缩合过程中加入1-20重量％亚硫酸氢钠而进行。现在已发现在固定的蜜胺与甲醛之比下较高的硫化物基团含量导致泡沫较高的甲醛散发量。因此所用预缩合物实际上应该不包含亚硫酸盐基，即亚硫酸盐基团含量应小于1％，优选小于0.1％，尤其是0。
需要加入乳化剂或乳化剂混合物以乳化发泡剂并稳定泡沫。阴离子、阳离子和非离子型表面活性剂及其混合物可用作乳化剂。
合适的阴离子表面活性剂为二苯并呋喃磺酸盐、链烷磺酸盐、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、酰基氨基链烷磺酸盐、酰基异硫代硫酸盐、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。可使用的非离子型表面活性剂为烷基苯酚聚乙二醇醚、脂肪醇聚乙二醇醚、脂肪酸聚乙二醇醚、脂肪酸链烷醇酰胺、EO/PO嵌段共聚物、氧化胺、甘油基脂肪酯、脱水山梨糖醇酯和烷基聚葡糖苷。可使用的阳离子型乳化剂为烷基三甲基铵盐、烷基苄基二甲基铵盐和烷基吡啶盐。乳化剂基于树脂优选以0.2-5重量％的量加入。
为由蜜胺树脂溶液生产泡沫，所述溶液必须包含发泡剂，其中量取决于所需的泡沫密度。原则上物理和化学发泡剂均可用于本发明方法。可行的物理发泡剂的实例为：液体形式的烃，卤代，尤其是氟代的烃，醇、醚、酮和酯，或作为气体的空气和CO2。合适的化学发泡剂例如为异氰酸酯与水的混合物，其中释放作为有效发泡剂的CO2，此外还有同样产生CO2的作为与酸的混合物的碳酸盐和碳酸氢盐，以及偶氮化合物如偶氮二甲酰胺。在本发明的优选实施方案中，将基于树脂为1-40重量％的具有0-80℃沸点的物理发泡剂加入水溶液或分散体中；在戊烷的情况下，优选5-15重量％。
所用固化剂为催化蜜胺树脂进一步缩合的酸性化合物。其量基于树脂为0.01-20重量％，优选0.05-5重量％。合适的是无机酸和有机酸，例如盐酸、硫酸、磷酸、硝酸、甲酸、乙酸、草酸、甲苯磺酸、氨基磺酸和酸酐。
水溶液或分散体优选不含其它添加剂。然而，为了某些目的，有利的是可基于树脂加入至多20重量％，优选小于10重量％的常规添加剂，例如染料、阻燃剂、UV稳定剂、降低燃烧气体毒性或促进碳化的试剂。因为泡沫通常为开孔泡沫且可吸收水，为了某些特定用途可能必须加入0.2-5重量％的防水剂。例如，聚硅氧烷、石蜡、聚硅氧烷和氟表面活性剂、疏水烃表面活性剂、聚硅氧烷和碳氟化合物乳液是合适的。
在预缩合物和溶剂的混合物中蜜胺/甲醛预缩合物的浓度可在55-85重量％，优选63-80重量％的宽范围内变化。优选预缩合物和溶剂的混合物的粘度为1-3000dPas，优选5-2000dPas。
使添加剂与蜜胺树脂的水溶液或分散体均匀混合，其中合适的话也可在加压下强制加入发泡剂。然而，也可起始于固态的，例如喷雾干燥的蜜胺树脂，然后将其与乳化剂、固化剂和发泡剂的水溶液混合。混合组分例如可在挤出机中进行。在混合之后，溶液或分散体通过喷嘴排出，随后直接加热并由此发泡。
加热含有发泡剂的溶液或分散体原则上可如EP-B 17671中所述通过热气体或高频辐照而进行。然而，根据EP-B 37470所需加热优选通过超高频辐照而进行。在该电介质辐照的情况下，原则上可使用0.2-100GHz频率范围内的微波。0.915、2.45和5.8GHz的频率可用于工业实践中，其中特别优选2.45GHz。电介质辐照的辐照源为磁控管，同时具有多个磁控管的辐照也是可以的。应确保的是在辐照过程中场分布尽可能均匀。
有利的是辐照以使得溶液或分散体的功率消耗基于溶液或分散体中1kg水为5-200kW，优选9-120kW的方式进行。如果吸收的功率较低，则发泡不再进行，且混合物仅仅固化。如果程序在优选范围内进行，则混合物发泡越快，功率消耗越大。每kg水大于约200kW时，发泡速率基本上不再增加。
待发泡混合物从产生泡沫的喷嘴中出现后，立即进行辐照。将由于温度升高和发泡剂蒸发而发泡的混合物施加至形成矩形管道的旋转带上，以使泡沫成型。
在生产本发明泡沫之后，对其进行热处理。通常在100-300℃，尤其是150-250℃下将其加热1-180分钟，优选5-60分钟，其中基本上除去水、发泡剂和甲醛。
根据本发明生产且优选实际上不包含亚硫酸盐基团的弹性泡沫具有5-50gl-1的密度。
如EP-B 37470中所述，可加热并模塑泡沫以改进其性能特征。
泡沫可生产为高度至多2m的板材或网状物(web)，或生产为具有几个mm厚度的泡沫片。当使用2.45GHz频率的微波时，优选的泡沫高度(在发泡方向上)为50-150cm。所有所需板材或片厚度可从这类泡沫网状物上切出。泡沫可在一侧或两侧配有或层压有盖板，例如纸、板、玻璃面毡、木材、石膏板、金属片或金属箔，或合适的话可经发泡的塑料膜。
根据本发明生产的泡沫的主要应用领域为建筑物和建筑物部件，尤其是隔板，也可为屋顶、外观、门和地板的热和声音隔绝；此外用于发动机机舱，车辆和飞机的内部的热和声音隔绝，以及用于例如冷藏室、油箱和液化气容器的低温隔绝。其它应用领域为作为隔绝墙覆盖层和隔绝和吸收震动包装材料的用途。由于交联的蜜胺树脂硬度很大，泡沫还可用于轻微的磨洗、研磨和抛光海绵。泡沫的开孔结构额外允许在泡沫内部吸附和储存合适的清洗剂、研磨剂和抛光剂。对于特定的清洗任务海绵还可提供有疏水和疏油处理。与目前市场上提供的M/F泡沫相比，由于本发明泡沫极低的甲醛散发量，其例如还可以薄的无纺织物形式，作为伤口绷带或者尿布和失禁产品的部件用于卫生领域。
实施例中所述份数和百分数基于重量。
实施例1
将70份喷雾干燥的蜜胺/甲醛预缩合物(摩尔比1∶1.6)和5.25份脲溶于水中。在每种情况下将基于树脂为3％的甲酸、2％的脂肪醇聚乙二醇醚和10％的戊烷加入该树脂溶液中。进行剧烈搅拌，随后通过经由在2.54GHz下辐照引入微波能量而在聚丙烯发泡模具中进行发泡。
甲醛捕捉剂在100-160℃温度下的加热过程中具有最大效果。在该温度下，泡沫仍未完全固化，以至于其保持可热成型性，然而其根据DIN 55666测量的甲醛散发量为0.1ppm或更少。因此本发明泡沫的甲醛散发量低于在“关于禁止化学品的规定”(the Regulation on Prohibited Chemicals)的§1中规定的0.1ppm的限度。
实施例
在110℃下加热之后，根据DIN 55666测得泡沫散发0.08ppm的甲醛。泡沫可热成型，但甲醛散发量低于“关于禁止化学品的规定”中的限度。
实施例2
重复实施例1，区别在于加热在220℃下进行，且根据DIN 55666测得0.3ppm的甲醛散发量。泡沫不可热成型。
对比例
重复实施例1，其中不加入脲。在110℃下加热之后，根据DIN 55666测得泡沫散发0.42ppm的甲醛。泡沫可热成型，但甲醛散发量高于“关于禁止化学品的规定”中的限度。
Claims (11)
1.一种通过使包含蜜胺/甲醛预缩合物、固化剂和发泡剂的混合物发泡并交联而加热生产泡沫的方法，其中在加热之前将基于蜜胺/甲醛预缩合物为2-10重量％的量的脲作为甲醛捕捉剂加入。
2.根据权利要求1的方法，其中所述混合物以包含55-85重量％蜜胺/甲醛预缩合物的水溶液或分散体的形式使用。
3.根据权利要求1的方法，其中预缩合物的蜜胺/甲醛摩尔比为1∶1.3-1∶4。
4.根据权利要求2的方法，其中预缩合物的蜜胺/甲醛摩尔比为1∶1.3-1∶4。
5.根据权利要求1-4中任一项的方法，其中基于蜜胺/甲醛预缩合物使用0.01-20重量％固化剂。
6.根据权利要求1-4中任一项的方法，其中基于蜜胺/甲醛预缩合物，以1-40重量％的量使用沸点为0-80℃的物理发泡剂。
7.根据权利要求5的方法，其中基于蜜胺/甲醛预缩合物，以1-40重量％的量使用沸点为0-80℃的物理发泡剂。
8.根据权利要求1-4中任一项的方法，其中在发泡和交联之后，在100-160℃的温度下加热所述泡沫。
9.根据权利要求5的方法，其中在发泡和交联之后，在100-160℃的温度下加热所述泡沫。
10.根据权利要求6的方法，其中在发泡和交联之后，在100-160℃的温度下加热所述泡沫。
11.根据权利要求7的方法，其中在发泡和交联之后，在100-160℃的温度下加热所述泡沫。
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| EP2616505B1 (de) * | 2010-09-16 | 2016-03-02 | Basf Se | Verfahren zur herstellung von melamin/formaldehyd-schaumstoffen |
| EP2630173B1 (en) | 2010-10-19 | 2015-01-07 | Borealis Agrolinz Melamine GmbH | Colloidal aminotriazine-aldehyde condensates and their use as aldehyde scavenger |
| DE102011009397A1 (de) | 2011-01-25 | 2012-07-26 | Basf Se | Verbundschaumstoff zur Schalldämmung |
| DE102012015128B4 (de) | 2012-07-30 | 2014-11-20 | Püschner GmbH + Co. KG | Verfahren und Vorrichtung zur Herstellung von harzbasierten Schaumstoffen |
| EP2703074A1 (de) | 2012-09-04 | 2014-03-05 | Basf Se | Verfahren zur Herstellung von Melamin/Formaldehyd-Schaumstoffen |
| CN102898778B (zh) * | 2012-09-07 | 2014-07-30 | 南通紫鑫实业有限公司 | 一种三聚氰胺甲醛树脂闭孔泡沫的制备方法 |
| EP2735584A1 (de) | 2012-11-26 | 2014-05-28 | Basf Se | Thermoverformbarer Melaminharzschaumstoff mit partikelförmigem Füllmaterial |
| DE102013217654B4 (de) | 2013-09-04 | 2017-02-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Formaldehydfreie Amino- oder Amidharze basierend auf einer reaktiven Schutzgruppe und einem Di- oder Trialdehyd als Netzwerkbildner |
| WO2015086074A1 (de) | 2013-12-12 | 2015-06-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Formaldehyd-freie harze basierend auf hydroxyaldehyden |
| WO2015086073A1 (de) | 2013-12-12 | 2015-06-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Formaldehyd-freie harze basierend auf glyoxylsäureestern |
| DE102015000393A1 (de) | 2014-01-21 | 2015-07-23 | Frank Becher | Verfahren zur Herstellung von geschlossen-porigen Erzeugnissen mit hohlen Zellen, mittels dessen der Druck in den Zellen kontrolliert während des Aufschäumens erhöht oder reduziert werden kann, sowie Erzeugnisse, die nach diesem Verfahren hergestellt werden |
| DE102014105093B4 (de) | 2014-04-10 | 2016-01-28 | Püschner Gmbh & Co. Kg | Verfahren und Mehrkammeranlage zur Herstellung von Keramikschäumen auf Basis von wässrigen Keramiksuspensionen und von harzbasierten Schaumstoffen |
| KR102176171B1 (ko) * | 2018-08-22 | 2020-11-09 | 주식회사 동성화학 | 내열성이 우수한 열성형성 멜라민 발포체 및 이의 제조방법 |
| WO2020221800A1 (en) | 2019-05-02 | 2020-11-05 | Basf Se | Melamine formaldehyde foam with reduced formaldehyde emission |
| KR102295346B1 (ko) * | 2019-07-17 | 2021-08-31 | 주식회사 동성케미컬 | 열성형성 멜라민 발포체 및 이의 제조 방법 |
| CN111234291B (zh) * | 2020-03-06 | 2022-09-20 | 郑州峰泰纳米材料有限公司 | 一种三聚氰胺甲醛树脂阻燃泡沫的制备方法 |
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| US5322915A (en) * | 1991-07-12 | 1994-06-21 | Basf Aktiengesellschaft | Modified melamine-formaldehyde resins |
| US20040097609A1 (en) * | 2000-09-27 | 2004-05-20 | Hans-Joachim Hahnle | Hydrophilic, open-cell, elastic foams with a melamine/formaldehyde resin base, production thereof and use thereof in hygiene products |
| CN1480253A (zh) * | 2003-04-10 | 2004-03-10 | 上海化工研究院 | 微胶囊包覆聚磷酸铵的制备方法 |
| US20050049321A1 (en) * | 2003-08-04 | 2005-03-03 | Horst Baumgartl | Shaped articles of melamine/formaldehyde foams having low formaldehyde emission |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080026605A (ko) | 2008-03-25 |
| DE102005027552A1 (de) | 2006-12-21 |
| ES2426344T3 (es) | 2013-10-22 |
| WO2006134083A1 (de) | 2006-12-21 |
| KR101328822B1 (ko) | 2013-11-13 |
| JP2008544005A (ja) | 2008-12-04 |
| US20080197524A1 (en) | 2008-08-21 |
| JP5284085B2 (ja) | 2013-09-11 |
| EP1893674A1 (de) | 2008-03-05 |
| PL1893674T3 (pl) | 2014-01-31 |
| EP1893674B1 (de) | 2013-08-14 |
| CN101198646A (zh) | 2008-06-11 |
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