CN103946287B - 基于酚树脂的泡沫材料 - Google Patents
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Abstract
本发明涉及基于酚树脂的泡沫材料及其用途。为了提供在基本上不改变泡沫性质的情况下具有改进的性质，尤其是具有改进的阻燃性的生物基热塑性泡沫材料，提出了一种泡沫材料，其通过至少下列步骤来制备：a)通过使至少一种酚系化合物与甲醛以1:1.0至1:3.0的比例，借助基于所使用的原料的量计为0.15重量％至5重量％的碱性催化剂在50℃至100℃的温度范围缩合，直至反应混合物的折射率为1.4990至1.5020来制备预聚物；并且随后b)在50℃至100℃的温度下，添加基于所使用的原料的量计为5重量％至40重量％的至少一种天然多酚；c)添加基于所使用的原料的量计为2重量％至10重量％的一种或更多种乳化剂和它们的混合物；d)添加基于所使用的原料的量计为2重量％至10重量％的一种或更多种发泡剂和它们的混合物；和e)添加基于所使用的原料的量计为10重量％至20重量％的固化剂；和f)固化。
Description
技术领域
本发明涉及基于酚树脂的泡沫材料及其用途。
背景技术
基于酚树脂的泡沫材料主要是在建筑领域和矿业以及隧道施工中用作密封和阻隔材料。
它们通常是基于水性甲阶酚醛树脂来制备的，将其在导入热或者没有导入热的情况下借助发泡剂和固化剂加工成酚树脂泡沫。
DE3718724描述了制备酚树脂泡沫的一般方法，其中首先将酚醛树脂与发泡剂、乳化剂和固化剂混合，该固化剂是无机酸或有机强酸。酸的选择取决于所期望的固化时间和温度。通常使用卤化的和非卤化的脂肪族烃作为发泡剂。
发明内容
本发明的任务在于，提供一种具有改进的性质，尤其是改进的阻燃性的生物基热塑性泡沫材料，同时基本上不改变泡沫性质。
根据本发明，所述任务通过由至少下列步骤制备的泡沫材料得以解决：
a)通过使至少一种酚系化合物与甲醛以1:1.0至1:3.0的比例，借助基于所使用的原料的量计为0.15重量％至5重量％的碱性催化剂在50℃至100℃的温度范围缩合，直至反应混合物的折射率为1.4990至1.5020来制备预聚物；并且随后
b)在50℃至100℃的温度下，添加基于所使用的原料的量计为5重量％至40重量％的至少一种天然多酚；
c)添加基于所使用的原料的量计为2重量％至10重量％的一种或更多种乳化剂和它们的混合物；
d)添加基于所使用的原料的量计为2重量％至10重量％的一种或更多种发泡剂和它们的混合物；和
e)添加基于所使用的原料的量计为10重量％至20重量％的固化剂；和
f)固化。
泡沫树脂通过酚、甲醛和一种或更多种来自天然酚类的可再生原料在碱性催化剂存在下的特定类型的缩合反应来获得(步骤a和b)。由这样的生物基树脂制备的泡沫材料(步骤c至e)显示出明显改进的阻燃性，其中其它的泡沫材料性质，例如导热性、耐磨强度、闭孔含量(Geschlossenzelligkeit)和抗压强度基本上保持不变，并且因此非常适合用于防火、耐热、耐寒和对噪音的保护。
这样实现预聚物的制备：将至少一种酚系化合物(例如选自苯酚和/或甲酚，其中出于简单易得的理由优选苯酚)与甲醛以1:1.0至1:3.0的比例以常规的方式和方法缩合。优选的是，所述比例为1:1.5至1:2.5，因为这样使得游离甲醛与苯酚的比例达到最佳平衡，并使最终产物中的单体含量降至最低。所述缩合在基于所使用的原料计为0.15重量％至5重量％，优选0.3重量％至1.5重量％的碱性催化剂的作用下进行，所述碱性催化剂例如是KOH、NaOH、Ba(OH)2、三乙胺。甲醛的添加在50℃至100℃的温度范围，在30min至150min的时间期间内进行。优选在75℃和85℃之间的温度和50min至70min的时间期间内，由此赋予对反应的最佳放热控制。如此调节所述缩合反应，使得反应混合物的折射率为1.4990至1.5020，优选为1.4995至1.5015。折射率是缩合程度的量度。借助阿贝折射仪在25℃按照DIN51423-2测量折射率。游离苯酚的含量已经<10％时是优选的，因此在最终产物中存在尽可能少的游离苯酚。
在进行酚系化合物与甲醛的反应之后，添加基于所使用的原料计为5重量％至40重量％的至少一种天然多酚，该天然多酚选自腰果壳油(CNSL，腰果壳液体)、碳水化合物、单宁(例如白坚木单宁)和它们的衍生物和/或木质素及其衍生物(例如木质素磺酸钠)。5重量％至20重量％的CNSL化合物、单宁化合物和/或木质素化合物是特别有利的，因为由此还可以明显改进制成的泡沫材料中的阻燃性，这使得产品的使用范围扩大。此外，CNSL化合物、单宁化合物和/或木质素化合物是天然的可再生原料，因而为环保地提供产品做出了贡献。天然的多酚在50℃至100℃、优选75℃至85℃的温度，在90min至210min、优选120至180min的时间内添加。
有利但非必需的是，随后冷却至40℃至70℃和减压蒸馏直至水含量为7％至20％，使得生物基泡沫树脂的粘度达到2000至14000mPas，这可以最优化的再加工成为可能。
来自步骤a)和b)的产物可以在低温下储存并在需要时使用。
在步骤c)中，在由步骤a)和b)中制备的根据本发明的、基于可再生原料的泡沫树脂中，混入基于所使用的原料的量计为2重量％至10重量％的一种或更多种乳化剂。优选使用的量为4重量％至8重量％。使用量在＜4重量％和＞8重量％时将不能均匀地混合，而是出现在步骤d)至e)中加入的添加剂的部分离析。该乳化剂可以选自环氧乙烷和/或环氧丙烷与饱和脂肪酸和不饱和脂肪酸、羟基脂肪酸、脂肪醇、甘油酯或植物油和/或邻苯二甲酸二甲酯、二乙二醇、邻苯二甲酸酐和/或它们的混合物的加合物。乳化剂或多种乳化剂的混合物在20℃到30℃的温度下混入。
之后在步骤d)中将一种或更多种发泡剂和/或它们的混合物以基于所使用的原料的量计为2重量％至10重量％，优选3重量％至8重量％混入。如果发泡剂的浓度<2重量％则树脂不发泡。发泡剂的量>10重量％时，固化期间模具中的压力过大且泡沫萎缩。发泡剂在15℃到25℃的温度下混入泡沫树脂中。作为发泡剂，使用现有技术中常规的物质，例如异丙基氯、异戊烷、环戊烷、丁烷、戊烷、己烷和/或庚烷和/或它们的混合物。
通过在步骤e)中混入基于所使用的原料的量计为10重量％至20重量％的一种或更多种固化剂(例如无机或有机酸如磷酸、硫酸、苯酚磺酸、对甲苯磺酸、二甲苯磺酸)，并将混合物导入模具中，在40℃到70℃的温度时以常规的方式固化根据本发明的泡沫材料(步骤f)。
一般来说可能的是，在步骤a)至e)中混入其它的添加剂，例如阻燃剂、加工助剂、增塑剂、中和剂或影响反应性的添加剂。
实施例
依据实施例来更详细阐释本发明：
实施例1-根据本发明的实施例泡沫树脂1)
在具有搅拌器的实验室反应器中，将100g苯酚与109.2g甲醛(45％浓度)和1.2g NaOH(50％浓度)混合。将所述溶液升温至80℃，并且进行缩合直至折射率为1.5002，游离苯酚的含量<10％。
在冷却之后添加20g溶剂型木质素(Organosolv-Lignin)，并将混合物保持在约80℃的温度直至使游离的苯酚含量<7.5％。之后进行减压蒸馏，直至水含量为15.7％。
实施例2-根据本发明的实施例(泡沫材料1)
在搅拌下向542g泡沫树脂1中，先后加入23g乙氧基化的蓖麻油、25g邻苯二甲酸二甲酯，以及59g的由85重量％异戊烷和15重量％环戊烷构成的发泡剂混合物。最后，搅拌加入118g固化剂，该固化剂由80重量％苯酚磺酸和20重量％磷酸(75％浓度)构成。
立即将反应混合物转移到预热至60℃的木质模具中，将该木质模具用木质盖子封闭并拧紧。将模具放置在调温至60℃的恒温器中。一个小时之后发泡过程结束，可以将泡沫材料脱模。
随后在恒温器中于60℃进行24小时的泡沫材料的后固化。
该泡沫材料具有下列性质：
密度＝36.2kg/m3
λ＝35.9mW/m*K
闭孔含量＝93.5％
阻燃性：自熄灭并且不发烟
剥落率(Abplatzrate)：1.0％/4:00min
实施例3-根据本发明的实施例(泡沫树脂2)
除了用热解木质素代替溶剂型木质素之外，完全重复实施例1。
实施例4-根据本发明的实施例(泡沫材料2)
与来自实施例2的配方相同地进行树脂4的发泡。泡沫材料具有下列性质：
密度＝47.5kg/m3
λ＝25.4mW/m*K
闭孔含量＝95.2％
阻燃性：自熄灭并且不发烟
剥落率：0.1％
实施例5-对比实施例(泡沫树脂3)
在具有搅拌器的实验室反应器中，将100g苯酚与109.2g甲醛(45％浓度)和1.2g NaOH(50％浓度)混合。将所述溶液升温至80℃，直至折射率为1.5476。
之后进行减压蒸馏，直至水含量为17.3％。
实施例6-对比实施例(泡沫材料3)
与来自实施例2的配方相同地进行树脂4的发泡。泡沫材料具有下列性质：
密度＝42.2kg/m3
λ＝23.0mW/m*K
闭孔含量＝100.0％
阻燃性：自熄灭并且不发烟
剥落率：14.2％/3:20min
实施例中的阻燃性借助于内部测量方法可再现地进行检验。为此，将样品点燃并且测量火焰穿透或样品的一部分剥落的时间。
总的来说可以确定的是，通过使用根据本发明的产品，可以明显改进阻燃性。这是不可预期的，因为来自现有技术已知的组合物(实施例5和6)示出了明显较差的剥落率。根据本发明的实施例在隔离性方面的性质与来自现有技术的那些是相当的。
Claims (10)
1.泡沫材料，其通过至少以下步骤制备：
a)通过使至少一种酚系化合物与甲醛以1:1.0至1:3.0的比例，借助基于所使用的原料的量计为0.15重量％至5重量％的碱性催化剂在50℃至100℃的温度范围缩合，直至反应混合物的折射率为1.4990至1.5020来制备预聚物；并且随后
b)在50℃至100℃的温度下，添加基于所使用的原料的量计为5重量％至40重量％的至少一种天然多酚；
c)添加基于所使用的原料的量计为2重量％至10重量％的一种或更多种乳化剂和它们的混合物；
d)添加基于所使用的原料的量计为2重量％至10重量％的一种或更多种发泡剂和它们的混合物；和
e)添加基于所使用的原料的量计为10重量％至20重量％的固化剂；和
f)固化。
2.根据权利要求1所述的泡沫材料，其特征在于，酚系化合物与甲醛的比例为1:1.5至1:2.5。
3.根据权利要求1或2所述的泡沫材料，其特征在于，步骤a)中制备的预聚物中游离的酚含量<10％。
4.根据权利要求1所述的泡沫材料，其特征在于，所述折射率为1.4995至1.5015。
5.根据权利要求1所述的泡沫材料，其特征在于，所述天然多酚选自丹宁化合物和/或木质素化合物和/或腰果壳油。
6.根据权利要求1所述的泡沫材料，其特征在于，所述天然多酚以基于所使用的原料的量为5重量％至20重量％的浓度添加。
7.根据权利要求1所述的泡沫材料，其特征在于，所述天然多酚在75℃至85℃的温度添加。
8.根据权利要求1所述的泡沫材料，其特征在于，所述乳化剂选自环氧乙烷和/或环氧丙烷与饱和脂肪酸和不饱和脂肪酸、羟基脂肪酸、脂肪醇、甘油酯或植物油和/或邻苯二甲酸二甲酯、二乙二醇、邻苯二甲酸酐和/或它们的混合物的加合物。
9.根据权利要求1所述的泡沫材料，其特征在于，所述发泡剂选自异丙基氯、异戊烷、环戊烷、丁烷、戊烷、己烷和/或庚烷和/或它们的混合物。
10.根据权利要求1-9中任一项所述的泡沫材料用于隔离和阻隔目的的用途。
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| CN103570900A (zh) * | 2013-10-08 | 2014-02-12 | 上海应用技术学院 | 一种酚醛树脂乳液的制备方法 |
| CN103554396A (zh) * | 2013-10-14 | 2014-02-05 | 中国林业科学研究院林产化学工业研究所 | 一种用于模塑料的木质素改性酚醛树脂的制备方法 |
| CN104311869A (zh) * | 2014-10-31 | 2015-01-28 | 武汉理工大学 | 一种酚醛泡沫制备的梯度发泡方法 |
| DE102015223556A1 (de) * | 2015-11-27 | 2017-06-01 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Schaumstoffe, die nachwachsende Rohstoffe enthalten, und deren Herstellung |
| FR3056986B1 (fr) * | 2016-10-04 | 2020-09-18 | Ceca Sa | Procede de fabrication de polyphenols alcoxyles |
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| CN115304728B (zh) * | 2021-05-08 | 2023-09-01 | 彤程化学（中国）有限公司 | 一种硫化树脂及其制备方法和应用 |
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