CN116733120A - 向结构提供隔离的方法 - Google Patents
向结构提供隔离的方法 Download PDFInfo
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- CN116733120A CN116733120A CN202310688507.XA CN202310688507A CN116733120A CN 116733120 A CN116733120 A CN 116733120A CN 202310688507 A CN202310688507 A CN 202310688507A CN 116733120 A CN116733120 A CN 116733120A
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Classifications
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- Inorganic Insulating Materials (AREA)
Abstract
本发明涉及一种为结构提供隔热和/或隔音的方法,包括以下步骤:‑提供基底,所述基底包括纤维;‑将所述基底施加到所述结构;‑在将所述基底施加到所述结构之前、期间或之后将所述基底与粘结剂组合物共混;‑在所述基底和所述粘结剂组合物已被施加到所述结构之后允许所述粘结剂组合物固化;其中所述粘结剂组合物包含至少一种水胶体。本发明还涉及可通过所述方法获得的隔离结构。
Description
本专利申请是申请号为201780028793X、申请日为2017年5月11日、发明名称为“向结构提供隔离的方法”的专利申请的分案申请。
技术领域
本发明涉及通过将包含纤维的基底施加到结构上并在将基底施加到结构之前、期间或之后将基底与粘结剂组合物共混来向结构提供隔热和/或隔音的方法。本发明还涉及可通过该方法获得的隔离结构。
背景技术
在许多施工项目中,向结构(例如,建筑物、建筑构件,诸如结构梁或建筑物的一部分)提供隔离材料是重要的考虑因素。提供隔热的材料可显著降低建筑物的能量需求,而提供隔音的材料可减少或消除不需要的外部噪声。一些隔离材料也改善了建筑物结构的耐火性。隔离材料通常包括颗粒材料和/或纤维,其提供隔离效果。
包含纤维的隔离材料具有许多不同的形式。例如,刚性形式诸如面板、絮垫和毯可被切割并放置在待隔离的结构中。另选地,其可为松散的填充或喷雾泡沫形式。
为了形成此类隔离产品,纤维—任选地与颗粒材料组合—通常粘结在一起。通常,粘结剂组合物与纤维和/或颗粒材料混合然后形成隔离产品例如面板、絮垫、毯或松散填充材料,该隔离产品随后被施加到该结构。
在建筑物的难以到达或具有非常规形状的部分中经常需要隔离产品。因此理想的是制备隔离材料,该隔离材料可以方便地现场喷涂或吹入结构的所需部分中。常用的隔离材料为用粘结剂提供的矿棉颗粒。通常,存在于待喷涂到结构上的隔离材料中的任何粘结剂组合物形成颗粒材料和/或纤维的一部分。例如,粘结剂组合物在早期加工阶段被添加到矿物纤维,因为它们通常在高温下凝固或固化。还已知在施用颗粒期间添加水玻璃。
在过去,可以经济地生产的苯酚甲醛树脂已被用作用于制备隔离材料的粘结剂组合物。然而,这些粘结剂受如下缺点的影响:它们包含甲醛并且它们因此处理起来可能有害从而在现场处理它们时需要保护措施。可用作粘合剂的非苯酚甲醛粘结剂是基于糖的粘结剂,例如在EP2990494A1、PCT/EP2015/080758、WO2007/014236、WO2011/138458和WO2009/080938中公开的组合物。
另一组非苯酚甲醛粘结剂为脂族和/或芳族酸酐与链烷醇胺的加成/消除反应产物,例如,如WO 99/36368、WO 01/05725、WO 01/96460、WO 02/06178、WO 2004/007615和WO2006/061249所公开的。这些粘结剂组合物是水溶性的,并且在固化速度和固化密度方面显示出优异的粘结特性。WO 2008/023032公开了该类型的脲改性粘结剂,其提供吸湿性降低的矿棉制品。
由于生产这些粘结剂所用的一些起始材料是相当昂贵的化学品,因此需要不断地提供能经济地生产的无甲醛粘结剂。
与先前已知的来自隔离材料的含水粘结剂组合物结合的另一个效果是,用于生产这些粘结剂的至少大部分起始材料源自化石燃料。消费者不断倾向于选择完全或至少部分地由可再生材料生产的产品,因此需要提供至少部分地由可再生材料生产的隔离材料粘结剂。
与先前已知的用于隔离材料的含水粘结剂组合物结合的另一个效果是,其包含腐蚀性和/或有害的组分。需要给隔离产品生产中涉及的机械采取防护措施,以防止腐蚀,也需要给操作这些机械的人员采取安全措施。这导致了成本增加和健康问题,因此需要提供具有降低含量的腐蚀性和/或有害材料的用于隔离产品的粘结剂组合物。
与先前已知的用于隔离材料的含水粘结剂组合物结合的再一个效果是,这些粘结剂通常与用于固化粘结剂的大规模固化设备相关联。通常,固化设备是在远远高于100℃,诸如200℃左右的温度下工作的炉,这与广泛的能量消耗有关。
此外,现有粘结剂组合物所需的广泛固化时间和高固化温度意味着传统粘结剂组合物必须与制造阶段即工厂中的纤维混合。不可能在现场即在施工阶段将粘结剂组合物与不含粘结剂的纤维混合。这是因为在现场创造所需的固化条件是不切实际且昂贵的。
除了对现场应用不切实际的固化条件之外,现有的粘结剂组合物诸如上文所讨论的那些通常在固化过程中产生有害物质。因此,任何现场固化都需要对进行固化的人员采取保护措施并进行专门培训。
发明内容
因此,本发明的目的是提供一种使用粘结剂组合物为结构提供隔热和/或隔音的方法,该粘结剂组合物含有可再生材料作为起始材料,并减少或消除腐蚀性和/或有害材料。
此外,本发明的目的是提供一种使用粘结剂组合物向结构提供隔热和/或隔音的方法,该粘结剂组合物不需要高温进行固化。
此外,本发明的目的是提供一种使用粘结剂组合物向结构提供隔热和/或隔音的方法,该粘结剂组合物可例如紧接在将隔离基底施加到结构之前、期间或之后现场施加到结构上,并且现场固化。
本发明的另一个目的是提供一种使用粘结剂组合物向结构提供隔热和/或隔音的方法,其中在粘结剂组合物的处理、施加和固化期间,尽可能地减少了对有害物质的暴露,并且不需要保护措施。
根据本发明的第一方面,提供了一种为结构提供隔热和/或隔音的方法,包括以下步骤:
-提供基底,该基底包括纤维;
-将基底施加到结构;
-在将基底施加到结构之前、期间或之后将基底与粘结剂组合物共混;-在基底和粘结剂组合物已被施加到结构之后允许粘结剂组合物固化;其中该粘结剂组合物包含至少一种水胶体。
根据本发明的第二方面,提供了通过根据本发明的第一方面的方法可获得的隔离结构。
本发明人惊奇地发现,如上所述,可以提供一种为结构提供隔热和/或隔音的方法,其中该粘结剂组合物可以在很大程度上由可再生材料制成,并且不含有或者仅较小程度地含有任何腐蚀性和/或有害物剂。
此外,本发明人惊奇地发现,由于用于本发明方法的粘结剂组合物通常不含任何有害物质,并且在固化过程中通常不释放任何有害物质,所以该方法可由任何人现场使用来实施,不用任何保护性措施且不需要专门培训实施该方法的人员。
此外,本发明人已惊奇地发现,用于本发明的粘结剂组合物不需要大量的固化时间或高固化温度;结果,可在现场将隔离材料施加到结构上,并且可允许粘结剂在现场固化。
具体实施方式
在本发明的第一方面中,为结构提供隔热和/或隔音的方法包括以下步骤:
-提供基底,该基底包括纤维;
-将基底施加到结构;
-在将基底施加到结构之前、期间或之后将基底与粘结剂组合物共混;-在基底和粘结剂组合物已被施加到结构之后允许粘结剂组合物固化;其中该粘结剂组合物包含至少一种水胶体。
可将隔热和/或隔音应用于任何结构。通常它是建筑物的一部分。在优选的实施方式中,待隔离的结构为建筑物或建筑物部件的墙壁、空腔壁、天花板、地板、阁楼或屋顶。
该基底包含纤维,并且优选地还包含颗粒材料。如果颗粒材料为气凝胶,则其可以高达45重量%至70重量%的量存在。可以最多至类似的重量%的量加入阻燃颗粒材料。
最优选地,包含纤维和任选颗粒材料的基底在与本发明的粘结剂组合物共混之前不包含初始粘结剂组合物。因此在这种情况下,最终隔离结构中的唯一粘结剂是根据本发明所需的粘结剂。
在一个实施方式中,该基底不包含矿棉。
矿棉基底通常包括人造玻璃质纤维(MMVF),例如玻璃纤维、陶瓷纤维、玄武岩纤维、渣棉、矿棉和石棉,其通过固化的矿棉粘结剂诸如热固性聚合物粘结剂材料粘结在一起。
天然纤维、合成纤维或天然纤维和合成纤维的组合可用于本发明。
合适的天然纤维可选自动物纤维(诸如绵羊毛)和植物纤维(诸如木丝、纤维素纤维、棉纤维、稻草、大麻、亚麻)。天然纤维优选不包括石棉。
合适的合成纤维可以是无机纤维、有机纤维或有机纤维和无机纤维的混合物。
合适的合成纤维可选自芳族聚酰胺纤维、聚丙烯腈(PAN)纤维、碳纤维、聚酯纤维和聚酰胺纤维。
优选地,纤维为无机的。最优选地,它们为矿物纤维,诸如玻璃纤维、陶瓷纤维或玄武岩纤维、渣纤维和石纤维。
在一个实施方式中,矿物纤维优选地为用粘结剂组合物粘结的纤维的颗粒屑形式。
在该实施方式中,屑为颗粒产品。颗粒产品通常通过生产固化的矿棉幅材然后使该幅材经受造粒过程从而形成颗粒来制备。该颗粒通常尺寸为1至5cm,并且粘结剂的含量相当于通常为1%左右的LOI值。然后将颗粒以压缩状态包装,并且在建筑物现场打开包装,以将颗粒产品用吹送设备施加到例如在墙壁或另一个结构之间的水平阁楼。
在施加颗粒产品之前或期间供应粘结剂组合物,从而将为矿棉元件的颗粒粘附到彼此。颗粒和粘结剂组合物提供了一种颗粒矿棉产品,其具有改进的特性,诸如容易减少灰尘并且提供不易于在其自身重量作用下塌陷的更具刚性的结构。
在另选的实施方式中,颗粒和粘结剂组合物提供了颗粒矿棉产品,其粘附到建筑物结构诸如墙壁或天花板上,使得矿棉产品完全或部分地涂覆建筑物结构。
然而,优选的是纤维为未粘结纤维的形式,使得最终隔离结构中的唯一粘结剂为根据本发明所需的粘结剂。
合适的颗粒材料可以是选自气凝胶、纤维素材料、珍珠岩、沸石锡石、蛭石和微球体中的一种或多种。在一个优选的实施方式中,颗粒材料为气凝胶、珍珠岩、蛭石、相变材料或阻燃剂。
一些纤维和颗粒,尤其是天然材料和合成有机纤维可对热敏感,例如,与无机纤维相比,这些材料中的一些具有相对低的熔融温度。与常规的相干复合材料相比,本发明的相干复合材料具有仍有可能使用热敏部件的有益效果,因为粘结剂不需要热进行固化。
在根据本发明提供隔离的方法中,粘结剂组合物包含至少一种水胶体。通常粘结剂组合物为含水组合物。
在一个优选的实施方式中,粘结剂组合物是无甲醛的。
就本专利申请的目的而言,术语“无甲醛”被定义为表征包含纤维的隔离产品,其中甲醛的排放低于由粘结剂粘结的基底块的5μg/m2/h,优选地低于3μg/m2/h。优选地,根据用于测试甲醛排放的ISO 16000进行测试。
根据本发明的由粘结剂粘结的基底的实施方式,令人惊奇的优点是其表现出自我修复特性。在暴露于非常恶劣的条件下,由粘结剂粘结的基底块松动其一部分强度之后,根据本发明的粘结的基底可重新获得初始强度的一部分或全部或甚至超过初始强度。在一个实施例中,老化强度是未老化强度的至少80%,诸如至少90%、诸如至少100%、诸如至少130%、诸如至少150%。这与常规的矿棉制品形成对比,其中暴露于恶劣环境条件之后的强度损失是不可逆的。
虽然不想受任何特定理论的束缚,但本发明人认为,根据本发明的包含纤维的隔离产品中的这种令人惊奇的特性是由于形成于固化粘结剂组合物的网络中键的复杂本性,该固化粘结剂组合物诸如是由含酚和/或醌的化合物所交联的蛋白质,或者是由酶交联的蛋白质,其还包括四级结构和氢键,允许在回到正常环境条件之后建立网络中的键。对于隔热产品,例如,当用作屋顶隔热时,其在夏季可暴露于非常高的温度,这对于产品的长期稳定性来说,是重要的优点。
水胶体
水胶体为植物、动物、微生物或合成来源的亲水性聚合物,通常包含许多羟基,并且可为聚电解质。水胶体广泛用于控制含水食品的功能特性。
水胶体可以是蛋白质或多糖,完全或部分地溶于水,并且主要用于増加连续相(水相)的粘度,即作为胶凝剂或増稠剂。水胶体还可用作乳化剂,这是因为其对乳液的稳定效应源自于水相的粘度增加。
水胶体通常由相似的但不相同的分子构成,这些分子由不同来源和制备方法产生。热处理以及例如盐含量、pH和温度均影响其展现的物理特性。水胶体的描述通常呈现理想化结构,但由于其是具有例如由随机酶作用确定,而不是由遗传密码精确制定(laydown)的结构的天然产物(或衍生物),因此结构可与理想结构不同。
许多水胶体为聚电解质(例如藻酸盐、明胶、羧甲基纤维素和黄原胶)。
聚电解质是其中大量重复单元具有电解质基团的聚合物。聚阳离子和聚阴离子为聚电解质。这些基团在水溶液(水)中解离,使聚合物带电。从而,聚电解质性质类似于电解质(盐)和聚合物(高分子量化合物),有时被称为聚盐。
带电基团确保尤其是每分子基础上的强力水合。反离子和共离子(与聚电解质具有相同电荷的离子)的存在引入离子特异性这一复杂性能。
反离子的比例与被捕集在其静电场中的聚电解质保持紧密关联,从而减少了反离子的活性和移动率。
在一个实施方式中,粘结剂组合物包含选自Mg2+、Ca2+、Sr2+、Ba2+的一种或多种反离子。
聚电解质的另一个特性是高线性电荷密度(每单位长度的带电基团数)。
通常,中性水胶体较不可溶,而聚电解质更可溶。
许多水胶体也凝胶。凝胶是显示类固体行为的含液态水的网络,其特征强度视其浓度而定,其硬度和脆度视所存在的一种或多种水胶体的结构而定。
水凝胶是能够溶胀以吸收和保持大量水的亲水性交联聚合物。水凝胶在卫生产品中的用途尤其已知。常用的材料使用聚丙烯酸酯,但水凝胶可通过交联可溶性水胶体,以制备不溶的但弹性的亲水性聚合物而制成。
水胶体的例子包括:琼脂、藻酸盐、阿拉伯木聚糖、卡拉胶、羧甲基纤维素、纤维素、凝胶多糖、明胶、结冷胶、β-葡聚糖、瓜尔胶、阿拉伯树胶、刺槐豆胶、果胶、淀粉、黄原胶。
在一个实施例中,该至少一种水胶体选自明胶、果胶、淀粉、藻酸盐、琼脂、卡拉胶、结冷胶、瓜尔豆胶、阿拉伯树胶、刺槐豆胶、黄原胶、纤维素衍生物诸如羧甲基纤维素、阿拉伯木聚糖、纤维素、凝胶多糖、β-葡聚糖构成的组。
聚电解水胶体的例子包括:明胶、果胶、藻酸盐、卡拉胶、阿拉伯树胶、黄原胶、纤维素衍生物诸如羧甲基纤维素。
在一个实施例中,至少一种水胶体为聚电解水胶体。
在一个实施例中,所述至少一种水胶体选自明胶、果胶、藻酸盐、卡拉胶、阿拉伯树胶、黄原胶、纤维素衍生物诸如羧甲基纤维素构成的组。
在一个实施例中,所述至少一种水胶体为凝胶形成剂。
在一个实施例中,至少一种水胶体是以盐,诸如Na+、K+、NH4+、Mg2+、Ca2+、Sr2+、Ba2+盐的形式使用。
明胶
明胶来源于胶原的化学降解。明胶为水溶性的,并且具有10.000至500.000g/mol,诸如30.000至300.000g/mol的分子量,分子量大小取决于水解等级。明胶是一种广泛使用的食物产品,因此人们普遍认为该化合物是完全无毒的,因此在处理明胶时不需要采取预防措施。
明胶是单链或多链多肽的异质混合物,通常显示螺旋结构。具体地讲,从作为明胶来源的皮肤和骨骼提取的I型胶原的三螺旋由两种α1(I)和一种α2(I)链组成。
明胶溶液可经历线圈螺旋转变。
A型明胶通过酸性处理产生。B型明胶通过碱性处理产生。
可将化学交联引入明胶。在一个实施例中,转谷氨酰胺酶用于将赖氨酸残基与谷氨酰胺残基连接;在一个实施例中,戊二醛用于将赖氨酸与赖氨酸连接,在一个实施例中,单宁用于连接赖氨酸残基。
明胶还可进一步水解成低至3000g/mol的较小片段。
在冷却明胶溶液时,可形成胶原样螺旋。
其他水胶体也可包含螺旋结构,诸如胶原样螺旋。明胶可形成螺旋结构。
在一个实施例中,包含水胶体的固化粘结剂包括螺旋结构。
在一个实施例中,该至少一种水胶体为低强度明胶,诸如具有30至125布卢姆(Bloom)凝胶强度的明胶。
在一个实施例中,该至少一种水胶体为中等强度明胶,诸如具有125至180布卢姆凝胶强度的明胶。
在一个实施例中,该至少一种水胶体为高强度明胶,诸如具有180至300布卢姆凝胶强度的明胶。
在一个优选的实施例中,明胶优选来来自哺乳动物、鸟类,诸如来自牛、猪、马、家禽和/或来自鱼鳞、鱼皮的一种或多种来源。
在一个实施例中,尿素可以加入到根据本发明的粘结剂组合物。本发明人已发现,即使是少量尿素的添加,也会导致明胶变性,这会减缓胶凝,这在一些实施方式中可能是合意的。尿素的添加也会导致产品的软化。
发明人已发现,明胶中的羧酸基团与三价离子和四价离子(例如,铝盐)强烈地相互作用。对于比A型明胶包含更多羧酸基团的B型明胶而言,尤其如此。
本发明人已发现,在一些实施例中,根据本发明的包含明胶的粘结剂组合物的固化/干燥不应在非常高的温度下开始。
本发明人已发现,在低温下开始固化可导致更强的产品。不受任何特定理论的束缚,本发明人假设在高温下开始固化可能造成粘结剂组合物外壳不可渗透,阻碍水从底部出来。
令人惊奇的是,根据本发明的包含明胶的粘结剂是非常耐热的。本发明人已发现,在一些实施例中,固化粘结剂可维持高达300℃的温度而不退化。
果胶
果胶是酸性结构多糖的异质分组,其存在于形成酸稳定凝胶的水果和蔬菜中。
通常,果胶不具有精确的结构,而是可包含多达17种不同单糖和超过20种不同类型的连接(linkage)。D半乳糖醛酸残基形成大多数分子。
凝胶强度随着Ca2+浓度的増加而増加,但随着温度和酸度増加(pH<3)而降低。
果胶可形成螺旋结构。
双阳离子的胶凝能力与藻酸盐发现的胶凝能力相似(Mg2+远小于Ca2+,Sr2+小于Ba2+)。
藻酸盐
藻酸盐是由褐色海藻产生的支架式多糖。
藻酸盐是包含β-(1,4)-连接的D-甘露糖醛酸(M)和α-(1,4)-连接的L-古洛糖醛酸(G)残基的直链非支链聚合物。藻酸盐也可以是细菌藻酸盐,另外诸如是O-乙酰化的。藻酸盐不是无规共聚物,但根据源藻类,由相似且严格交替的残基(即MMMMMM、GGGGGG和GMGMGMGM)的嵌段组成,每个残基具有不同的构象偏好和行为。藻酸盐可以用宽范围的平均分子重量(50至100000个残基)制备。游离羧酸具有牢固地氢键键合至羧酸根的水分子H3O+。Ca2+离子可置换这种氢键键合,拉动(zipping)古洛糖醛酸,而不是甘露糖醛酸,在所谓的蛋盒状构象中以化学计量地链接到一起。具有不同特异性的重组差向异构酶可用于产生设计的(designer)藻酸盐。
藻酸盐可形成螺旋结构。
卡拉胶
卡拉胶是从红色海藻碱性提取(和改性)制备的支架式多糖的统称。
卡拉胶是约25,000个半乳糖衍生物的线性聚合物,取决于来源和提取条件,具有规则但不确切的结构。
κ-卡拉胶(卡帕型卡拉胶)通过主要从热带海藻长心卡帕藻(也称为耳突麒麟菜)分离的μ-卡拉胶的碱性消除来制备。
Ι-卡拉胶(约塔型卡拉胶)通过主要从菲律宾海藻齿麒麟菜(也称为刺麒麟菜)分离的ν-卡拉胶的碱性消除来制备。
λ-卡拉胶(拉姆达型卡拉胶)(主要从皱波角叉菜(Gigartina pistillata)或爱尔兰海藻(Chondrus crispus)分离)通过碱性消除转化成θ-卡拉胶(西塔型卡拉胶),但比Ι-卡拉胶和κ-卡拉胶产量要慢得多。
κ-卡拉胶的最强凝胶由K+而非Li+、Na+、Mg2+、Ca2+或Sr2+形成。
所有卡拉胶可形成螺旋结构。
阿拉伯树胶
阿拉伯树胶是阿拉伯半乳糖寡糖、多聚糖和糖蛋白的复杂可变的混合物。阿拉伯树胶由较低相对分子质量的多糖和较高分子量的富含较宽可变性羟基脯氨酸的糖蛋白的混合物组成。
阿拉伯树胶同时存在亲水性碳水化合物和疏水性蛋白质。
黄原胶
黄原胶是由例如野油菜黄单胞菌(Xanthomonas campestris)的有氧深层发酵制备的微生物耐干燥(desiccation-resistant)聚合物。
黄原胶是具有β-(1,4)-D-吡喃葡萄糖葡聚糖(作为纤维素)主链与-(3,1)-α-连接的D-吡喃甘露糖-(2,1)-β-D-葡萄糖醛酸-(4,1)-β-D-吡喃甘露糖侧链在交替残基上的阴离子聚电解质。
已经提出了黄原胶天然状态为双分子反平行双螺旋。有序双螺旋构象和更灵活的单伸展链之间的转换可能发生在40℃至80℃之间。
黄原胶可形成螺旋结构。
黄原胶可包含纤维素。
纤维素衍生物
纤维素衍生物的一个实例是羧甲基纤维素。
羧甲基纤维素(CMC)是由纤维素与碱和氯乙酸反应形成的纤维素的化学改性衍生物。
CMC结构基于纤维素的β-(1,4)-D-吡喃葡萄糖聚合物。不同制剂可具有不同的取代程度,但通常在每个单体单元0.6至0.95个的衍生物的范围内。
琼脂
琼脂是由同科红色海藻(Rhodophycae)作为卡拉胶制备的支架式多糖。琼脂可从石花菜和江蓠菜(Gracilariae)的物种商购获得。
琼脂由琼脂糖和琼脂胶的混合物组成。琼脂糖是基于-(1,3)-β-D-吡喃半乳糖-(1,4)-3,6-内醚-α-L-吡喃半乳糖单元的相对分子质量(分子量)约120,000的线性聚合物。
琼脂胶是较少量的较小分子的异质混合物。
琼脂可形成螺旋结构。
阿拉伯木聚糖
阿拉伯木聚糖天然存在于草的麸皮(Graminiae)中。
阿拉伯木聚糖由连接到β-(1,4)-连接的D-吡喃木糖聚合物主链作为分支点的α-L-阿拉伯呋喃糖残基组成。
阿拉伯木聚糖可形成螺旋结构。
纤维素
纤维素是在植物中作为微纤维(2-20nm的直径和100-40 000nm长)发现的支架式多糖。纤维素主要是由木浆制备。纤维素也由一些细菌(例如,木醋杆菌)以高度水合形式生成。
纤维素是β-(1,4)-D-吡喃葡萄糖单元在4C1构象中的线性聚合物。存在四种结晶形式:Iα、Iβ、II和III。
纤维素衍生物可为甲基纤维素、羟丙基甲基纤维素、羟乙基甲基纤维素、羟乙基纤维素、羟丙基纤维素。
凝胶多糖
凝胶多糖(Curdlan)是从粪产碱杆菌(Alcaligenes faecalis var.myxogenes)的突变菌株商业上制备的聚合物。凝胶多糖(可得然胶)是中等相对分子质量,直链非支链的1,3β-D葡聚糖,且不具有侧链。
凝胶多糖可形成螺旋结构。
可得然胶不溶于冷水中,但含水悬浮液在加热至约55℃产生可逆凝胶之前増塑并短暂溶解。在较高温度下加热产生更有回弹力的不可逆凝胶,不可逆凝胶随后保持冷却。
硬葡聚糖也是1,3β-D葡聚糖,但具有在环境条件下赋予可溶性的额外的1,6β-连接。
结冷胶
结冷胶是直链四糖4)-L-鼠李糖基-(α-1,3)-D-吡喃葡萄糖基-(β-1,4)-D-吡喃葡糖醛酸基-(β-1,4)-D-吡喃葡萄糖基-(β-1,其中在3-连接的葡萄糖上具有O(2)L-甘油基和O(6)乙酰基取代基。
结冷胶可形成螺旋结构。
β-葡聚糖
β-葡聚糖存在于草的麸皮(禾本科(Gramineae))中。
β-葡聚糖由连接的β-(1,3)-和β-(1,4)-D-吡喃葡萄糖单元的直链非支链多糖以非重复但非随机顺序组成。
瓜尔胶
瓜尔胶(也称为瓜拉那)是从豆科灌木瓜尔豆的种子提取的储备多糖(种子粉)。
瓜尔胶是与刺槐豆胶类似的半乳甘露聚糖,由(1,4)-连接的β-D-吡喃甘露糖主链组成,其6位分支点连接至α-D-半乳糖(即,1,6-连接的α-D-吡喃半乳糖)。
瓜尔胶由非离子型多分散棒状聚合物形成。
与刺槐豆胶不同,瓜尔胶不形成凝胶。
刺槐豆胶
刺槐豆胶(也称为角豆胶和卡如宾)是从角豆树(Ceratonia siliqua)的种子(内核)提取的储备多糖(种子粉)。
刺槐豆胶是与瓜尔胶类似的半乳甘露聚糖,由(1,4)-连接的β-D-葡萄糖醛酸主链组成,其6位分支点连接至α-D-半乳糖(即1,6-连接的-α-D-吡喃半乳糖)。
刺槐豆胶是由非离子分子组成的多分散体。
淀粉
淀粉由两种类型的分子,直链淀粉(通常20-30%)和支链淀粉(通常70-80%)组成。这两者均由4C1构象中α-D-葡萄糖单元的聚合物组成。在直链淀粉中,其连接方式为-(1,4)-,其环氧原子都在同一侧,而在支链淀粉中,大概每二十个单元约一个残基也连接有-(1,6)-,形成了分支点。直链淀粉对支链淀粉和-(1,6)-分支点的相对比例均取决于淀粉来源。淀粉可来源于谷物(玉米)、小麦、马铃薯、木薯和大米。支链淀粉(不含直链淀粉)可从‘蜡质’玉米淀粉分离出来,在用支链淀粉酶特异性水解支链淀粉后,最佳分离出直链淀粉(不含支链淀粉)。
直链淀粉可形成螺旋结构。
在一个实施例中,至少一种水胶体为淀粉的功能性衍生物,诸如交联,氧化,乙酰化,羟丙基化和部分水解的淀粉。
在一个优选的实施例中,粘结剂组合物包含至少两种水胶体,其中一种水胶体为明胶,并且所述至少一种其他水胶体选自果胶、淀粉、藻酸盐、琼脂、卡拉胶、结冷胶、瓜尔豆胶、阿拉伯树胶、刺槐豆胶、黄原胶、纤维素衍生物诸如羧甲基纤维素、阿拉伯木聚糖、纤维素、凝胶多糖、β-葡聚糖构成的组。
在一个实施例中,粘结剂组合物包含至少两种水胶体,其中一种水胶体为明胶,并且至少其他水胶体为果胶。
在一个实施方式中,粘结剂组合物包含至少两种水胶体,其中一种水胶体为明胶,并且至少一种其他水胶体为藻酸盐。
在一个实施方式中,粘结剂组合物包含至少两种水胶体,其中一种水胶体为明胶,并且至少一种其他水胶体为羧甲基纤维素。
在一个优选的实施方式中,根据本发明的粘结剂组合物包含至少两种水胶体,其中一种水胶体为明胶,并且其中明胶基于水胶体的重量计,以10重量%至95重量%,诸如20重量%至80重量%、诸如30重量%至70重量%、诸如40重量%至60重量%的量存在于该粘结剂组合物中。
在一个实施方式中,粘结剂组合物包含至少两种水胶体,其中一种水胶体和至少一种其他水胶体具有互补的电荷。
在一个实施例中,一种水胶体为明胶或阿拉伯树胶中的一种或多种,其与选自果胶、藻酸盐、卡拉胶、黄原胶或羧甲基纤维素的一种或多种水胶体具有互补的电荷。
在一个实施例中,粘结剂组合物能够在不超过95℃,诸如5至95℃、诸如10至80℃、诸如20至60℃、诸如40至50℃的温度下固化。
在一个实施方式中,根据本发明的粘结剂组合物不是热固性粘结剂。
热固性组合物处于软固体或粘稠液体状态,优选包含预聚物,优选包含树脂,通过固化不可逆地转变为不可熔的、不溶性聚合物网络。固化通常由热作用引起,由此通常需要高于95℃的温度。
固化的热固性树脂被称为热固性或热固性塑料/聚合物—当用作聚合物复合材料中的主体材料时,其被称为热固性聚合物基质。在一个实施例中,根据本发明的含水粘结剂组合物不包含聚(甲基)丙烯酸,聚(甲基)丙烯酸或聚(甲基)丙烯酸的酯。
在一个实施例中,至少一种水胶体为生物聚合物或改性的生物聚合物。
生物聚合物是由活生物体产生的聚合物。生物聚合物可包含共价键合以形成较大结构的单体单元。
根据所用单体单元和形成的生物聚合物的结构,生物聚合物被划分成三种主要类别:多核苷酸(RNA和DNA),其是由13个或更多个核苷酸单体组成的长聚合物;多肽(诸如蛋白质),其为氨基酸的聚合物;多糖,诸如线性键合的聚合碳水化合物结构。
多糖可以是线性或支化的;多糖通常与糖苷键连接。另外,许多糖单元可经过各种化学改性,形成其他分子,诸如糖蛋白的部分。
在一个实施例中,至少一种水胶体为生物聚合物或改性的生物聚合物,其具有1,诸如0.9至1的分子量分布的多分散性指数。
在一个实施例中,粘结剂组合物包含动物来源的蛋白质,包括胶原、明胶和水解明胶,并且所述粘结剂组合物还包含至少一种含酚和/或醌的化合物,诸如选自单宁酸、缩合单宁(原花青素)、可水解单宁、没食子单宁、鞣花单宁、复合单宁构成的组中的一种或多种组分的单宁,和/或源自橡树、栗树、火炬树和大穗杯花中的一种或多种的单宁。
在一个实施例中,粘结剂组合物包含动物来源的蛋白质,包括胶原、明胶和水解明胶,并且其中所述粘结剂组合物还包含至少一种酶,所述至少一种酶选自转谷氨酰胺酶(EC2.3.2.13)、蛋白质二硫键异构酶(EC 5.3.4.1)、硫醇氧化酶(EC 1.8.3.2)、多酚氧化酶(EC1.14.18.1),特别是儿茶酚氧化酶、酪氨酸氧化酶和酚氧化酶、赖氨酰氧化酶(EC1.4.3.13)和过氧化物酶(EC 1.11.1.7)构成的组。
在一个实施例中,粘结剂组合物是无甲醛的。
在一个实施例中,根据本发明的粘结剂组合物基本上由下列组成:
-至少一种水胶体;
-任选地至少一种油;
-任选地至少一种pH调节剂;
-任选地至少一种交联剂;
-任选地至少一种防污剂;
-任选地至少一种抗溶胀剂;
-水。
在一个实施例中,该至少一种油为非乳化的烃油。
在一个实施例中,该至少一种油为乳化的烃油。
在一个实施例中,该至少一种油为基于植物的油。
在一个实施例中,至少一种交联剂选自单宁酸、缩合单宁(原花青素)、可水解单宁、没食子单宁、鞣花单宁、复合单宁构成的组中的一种或多种组分的单宁,和/或源自橡树、栗树、火炬树和大穗杯花中的一种或多种的单宁。
在一个实施例中,该至少一种交联剂是选自转谷氨酰胺酶(EC 2.3.2.13)、蛋白质二硫键异构酶(EC 5.3.4.1)、硫醇氧化酶(EC 1.8.3.2)、多酚氧化酶(EC 1.14.18.1),特别是儿茶酚氧化酶、酪氨酸氧化酶和酚氧化酶、赖氨酰氧化酶(EC 1.4.3.13)和过氧化物酶(EC 1.11.1.7)构成的组的酶。
在一个实施例中,至少一种抗溶胀剂是单宁酸和/或单宁。
在一个实施例中,至少一种防污剂是一种抗微生物剂。
抗微生物剂可为苯甲酸、丙酸、苯甲酸钠、山梨酸和山梨酸钾,以抑制细菌和真菌细胞的生长。然而,可以使用天然生物防腐剂。壳聚糖被认为是抗真菌和抗菌的。最频繁使用的抗微生物的生物防腐剂是溶菌酶和乳酸链球菌肽。可使用的常见其他生物防腐剂为细菌素,诸如乳链球菌素和片球菌素和抗微生物酶,诸如几丁质酶和葡萄糖氧化酶。另外,乳过氧化物酶(LPS)的使用呈现抗真菌和抗病毒活性。也可使用不同浓度的天然抗微生物剂,诸如单宁、迷迭香和大蒜精油、牛至油、柠檬草或肉桂油。
在一个实施方式中,至少一种水胶体基于粘结剂组合物的重量计,以1重量%至50重量%诸如2.5重量%至25重量%的量存在于粘结剂组合物中。
在一个实施例中,明胶基于水胶体的重量计,以10至95重量%,诸如20至80重量%、诸如30至70重量%、诸如40至60重量%的量存在于含水粘结剂组合物中。
在根据本发明提供隔热和/或隔音的方法中,粘结剂组合物在将基底施加到结构之前、期间或之后与基底共混。
当粘结剂组合物在将基底施加到结构之前与基底共混时,共混步骤优选发生在将混合物(混合物为共混在一起的基底和粘结剂组合物)施加到结构之前不超过20分钟,更优选不超过10分钟,最优选不超过5分钟。这在将混合物施加到待隔离的结构之前最小化粘结剂组合物的固化。
当粘结剂组合物在施加到结构期间与基底共混时,优选将粘结剂组合物和基底同时施加到结构上。
在一个优选的实施方式中,通过喷涂、吹送或倾倒将基底和粘结剂组合物施加到所述结构。
最优选地,通过喷涂同时施加粘结剂组合物和基底。这可例如通过将基底和粘结剂组合物共混以形成混合物,然后通过一个或多个喷嘴喷涂所述混合物。另选地,一个或多个基底和粘结剂组合物可从单独的喷嘴喷出以形成单一共混料流,其被施加到结构。作为另一个选项,两个或更多个料流可在施加到结构上时共混。
当基底包含两种或更多种组分时,这些组分可在与粘结剂组合物共混之前共混,或单独但同时施用,用于上文给出的基底和粘结剂组合物选项。
在其中粘结剂组合物包含两种或更多种组分的实施方式中,它们通常在与基底进一步共混之前共混。然而,也可以将它们单独施加,用于上文给出的基底和粘结剂组合物选项。
当粘结剂组合物在将基底施加到结构之后与基底共混时,共混步骤优选发生在将基底施加到结构之后不超过20分钟,更优选不超过10分钟,最优选不超过5分钟。这最小化了粘结剂在基底和粘结剂已完全共混之前的固化。
在适当的情况下,将基底和粘结剂组合物施加到结构的至少一个表面上,例如至少一个壁。另选地,可将基底和粘结剂组合物施加到结构中的空腔或空间,诸如空腔壁。
在本发明的方法中,使粘结剂组合物在将基底和粘结剂组合物施加到结构之后固化。优选地,使粘结剂组合物在环境温度下固化,即在结构的场地处存在的温度下固化,而不施用热源。环境温度可以是10℃至40℃。在另一个优选的实施方式中,粘结剂施加的固化优选在5℃至95℃,诸如5℃至80℃,诸如8℃至50℃,更优选10℃至40℃的温度下进行。如果希望在不同于环境温度的温度下固化,可以加热或冷却结构或其周围环境。
优选地,固化步骤发生在数分钟或数小时后。
固化被定义为一个粘结剂组合物经受物理和/或化学反应,通常直到粘结剂组合物达到固态的过程,其中,化学反应的情况通常増大粘结剂组合物中化合物的分子量并由此増加粘结剂组合物的粘度。
在一个实施例中,固化过程包括交联和/或水作为结晶水的加入(inclusion)。
在一个实施例中,固化的粘结剂含有含量取决于主导的温度、压力和湿度条件可能会降低并升高的结晶水。
在一个实施例中,固化过程包括压力干燥。可通过吹空气或气体越过/穿过纤维和任选颗粒材料和粘结剂的混合物来施加压力。吹塑方法可伴随加热或冷却,或其可处于环境温度下。
在一个实施例中,固化过程在潮湿环境中进行。潮湿环境可具有60至99%,诸如70至95%、诸如80至92%相对湿度RH。在潮湿环境下的固化可跟随有固化或干燥,以获得普遍的湿度状态。
一旦该粘结剂组合物被固化,则基底和粘结剂组合物的混合物出现相干。
基底和固化的粘结剂组合物的共混物优选具有10至900kg/m3的密度。
用作隔音材料(例如,吸声),基底和固化粘结剂组合物的共混物可具有60至200kg/m3,优选80至150kg/m3的密度。
吸声可被定义为加权吸声系数αω≥0.8的材料(吸收等级A和B-EN ISO 11654)。
用作隔热材料,基底和固化粘结剂组合物的共混物可具有10至200kg/m3,优选30至100kg/m3的密度。
隔热可被定义为具有在10℃下λ≤0.060W/m K的λ值的材料。
本发明还涉及通过上述方法可获得的隔离结构。具体地讲,本发明的第二方面是可通过以下步骤获得的隔离结构:
-提供基底,该基底包括纤维;
-将基底施加到结构;
在将基底施加到结构之前、期间或之后将基底与粘结剂组合物共混;
-在基底和粘结剂组合物已被施加到结构之后允许粘结剂组合物固化;
其中该粘结剂组合物包含至少一种水胶体。
隔离结构可以是任何结构,但优选地为建筑物或建筑物部件的墙壁、空腔壁、天花板、地板、阁楼或屋顶
。隔离结构优选地提供隔热和/或隔音。
在本发明的该方面中,可应用上文关于第一方面讨论的任何特征。
根据本发明制成的隔离产品包括包含水胶体的粘结剂组合物的固化所产生的粘结剂,如在本发明的第一方面中所述的。
在一个实施方式中,根据本发明的由粘结剂粘结的基底块的烧失量(LOI)按重量计,在0.1%至25.0%,诸如0.3%至18.0%、诸如0.5%至12.0%、诸如0.7%至8.0%的范围内。
基于基底的重量计,隔离产品在基底中的粘结剂固体的重量%可为0.1%至50.0%,诸如0.3%至36.0%、诸如0.5%至24.0%、诸如0.7%至16.0%、诸如1.4%至12.0%、诸如2.0%至8.0%。
在一个实施例中,粘结剂是不交联的。
在一个替代的实施例中,粘结剂是交联的。
粘结剂组分的反应
本发明人已发现,在一些实施方式中,根据本发明的隔离制品当粘结剂在酸性条件下施加到基底时是制备得最好的。因此,在一个优选的实施方式中,施加到基底的粘结剂包含pH调节剂,特别是以pH缓冲剂的形式。
在一个优选的实施例中,未固化状态的粘结剂具有小于8,诸如小于7、诸如小于6的pH值。
本发明人已发现,在一些实施例中,粘结剂的固化在碱性条件下被强烈地加快。因此,在一个实施方式中,粘结剂组合物包含pH调节剂,优选以碱诸如有机碱(诸如其胺或盐)、无机碱诸如金属氢氧化物(诸如KOH或NaOH)、其氨或盐的形式。
在一个特定的优选实施例中,pH调节剂为碱金属氢氧化物,特别是NaOH。
在一个优选的实施例中,根据本发明的粘结剂组合物具有7至10,诸如7.5至9.5、诸如8至9的pH。
其它添加剂可为诸如一种或多种反应性或非反应性硅氧烷的组分,并且可加入到粘结剂中。优选地,一种或多种反应性或非反应性硅氧烷选自由有机硅氧烷残基,尤其是二苯基硅氧烷残基、烷基硅氧烷残基,优选二甲基硅氧烷残基组成的主链,其具有至少一种羟基、酰基、羧基或酸酐、胺、环氧基或乙烯基官能团,能够与粘结剂组合物的至少一种组分反应并优选地,以粘结剂的总质量计,以0.1重量%至15重量%,优选0.1重量%至10重量%,更优选0.3重量%至8重量%的量存在。
在一个实施例中,可将油添加到粘结剂组合物中。
在一个实施例中,该至少一种油为非乳化的烃油。
在一个实施例中,该至少一种油为乳化的烃油。
在一个实施例中,该至少一种油为基于植物的油。
在一个实施例中,至少一种交联剂选自单宁酸、缩合单宁(原花青素)、可水解单宁、没食子单宁、鞣花单宁、复合单宁构成的组中的一种或多种组分的单宁,和/或源自橡树、栗树、火炬树和大穗杯花中的一种或多种的单宁。
在一个实施例中,该至少一种交联剂是选自转谷氨酰胺酶(EC 2.3.2.13)、蛋白质二硫键异构酶(EC 5.3.4.1)、硫醇氧化酶(EC 1.8.3.2)、多酚氧化酶(EC 1.14.18.1),特别是儿茶酚氧化酶、酪氨酸氧化酶和酚氧化酶、赖氨酰氧化酶(EC 1.4.3.13)和过氧化物酶(EC 1.11.1.7)构成的组的酶。
在一个实施例中,至少一种抗溶胀剂是单宁酸和/或单宁。
在一个实施例中,至少一种防污剂是一种抗微生物剂。抗微生物剂可为苯甲酸、丙酸、苯甲酸钠、山梨酸和山梨酸钾,以抑制细菌和真菌细胞的生长。然而,可以使用天然生物防腐剂。壳聚糖被认为是抗真菌和抗菌的。最频繁使用的抗微生物的生物防腐剂是溶菌酶和乳酸链球菌肽。可使用的常见其他生物防腐剂为细菌素,诸如乳链球菌素和片球菌素和抗微生物酶,诸如几丁质酶和葡萄糖氧化酶。另外,乳过氧化物酶(LPS)的使用呈现抗真菌和抗病毒活性。也可使用不同浓度的天然抗微生物剂,诸如单宁、迷迭香和大蒜精油、牛至油、柠檬草或肉桂油。
在一个实施例中,粘结剂中可加入防污剂。
在一个优选的实施例中,防污剂是单宁,特别是选自单宁酸、缩合单宁(原花青素)、可水解单宁、没食子单宁、鞣花单宁、复合单宁构成的组中的一种或多种组分的单宁,和/或源自橡树、栗树、火炬树和大穗杯花中的一种或多种的单宁。
在一个实施例中,粘结剂中可加入抗溶胀剂,诸如单宁酸和/或单宁。
另外的添加剂可为包含钙离子和抗氧化剂的添加剂。
在一个实施例中,根据本发明的粘结剂组合物包含接头(linker)形式的添加剂,该接头包含酰基和/或胺基和/或硫醇基。这些接头可以増强和/或修饰固化粘结剂的网络。
在一个实施例中,根据本发明的粘结剂组合物包含选自PEG型试剂、硅烷和羟基磷灰石的另外的添加剂。
实施例
在下列实例中,制备落入本发明定义的几种粘结剂,并且与根据现有技术的粘结剂进行比较。
根据现有技术的粘结剂
测定根据现有技术的粘结剂的以下特性。
试剂
硅烷(Momentive VS-142)由迈图(Momentive)公司提供,并且为了简化,以100%计算。所有其他组分由西格玛奥德里奇公司(Sigma-Aldrich)以高纯度提供,并且为了简化,假定为无水的,除非另外说明。
粘结剂组分固体含量—定义
固化前,给定粘结剂溶液中每种组分的含量基于组分的无水质量。可使用以下公式:
粘结剂组分固体含量(%)=粘结剂组分A固体(g)+粘结剂组分B固体(g)+……/混合物总重量(g)×100%(%)
粘结剂固体—定义和过程
固化后粘结剂的含量被称为“粘结剂固体”。
圆盘形石棉样品(直径:5cm;高度1cm)从石棉切割出来,并且在580℃下热处理至少30分钟以除去所有有机物。通过将粘结剂混合物(约2g)的样品分配到锡箔容器中的经热处理的石棉盘上测量粘结剂混合物的固体(参见下文用于混合的实例)。在直接加入粘结剂混合物之前和之后,称取包含石棉盘的锡箔容器的重量。制备在锡箔容器中石棉盘装入的两种此类粘结剂混合物,然后将它们在200℃下加热1小时。在冷却并在室温下储存10分钟后,将样品称重,并且将粘结剂固体计算为两个结果的平均值。然后,通过用需要的水量和10%的硅烷水溶液(Momentive VS-142)来制备具有所需粘结剂固体的粘结剂。
反应损失—定义
反应损失被定义为粘结剂组分固体含量和粘结剂固体之间的差值。
机械强度研究(条测试)—过程
在条(bar)测试中测试粘结剂的机械强度。对于每种粘结剂,由粘结剂和来自石棉纺丝生产的石棉丸的混合物制造16个条。所述丸是与石棉纤维具有相同熔融组合物的颗粒,并且通常被认为是来自纺丝工艺的废产物。用于条状组合物的丸的尺寸为0.25至0.50毫米。
如上文“粘结剂固体”所述,获得包含0.5%硅烷(Momentive VS-142)的15%粘结剂固体的粘结剂溶液。将该粘结剂溶液的样品(16.0g)与丸(80.0g)混合。所得混合物然后被均分成四个插槽形成在一个耐热硅树脂用于制造小条(4×5插槽形式;插槽顶部尺寸:长度=5.6厘米,宽度=2.5厘米;槽底尺寸:长度=5.3厘米,宽度=2.2厘米;插槽高度=1.1厘米)。然后将放置在插槽中的混合物用适当尺寸的平坦金属条压硬以产生均匀条表面。以此方式制得来自每个粘结剂的16个条。然后将所得的条在200℃下固化1h。冷却至室温后,将条小心地取出容器。在高压釜内老化16个条中的八个(15分钟/120℃/1.2巴)。
干燥1至2天后,所有的条在3点弯曲测试中发生断裂(测试速度:10.0mm/min;破裂水平:50%;标称强度:30N/mm2;支持距离:40mm;最大挠曲20mm;标称e模块10000N/mm2)在弯曲电车站(Bent Tram machine)上,研究其机械强度。将条放置在机器中的“顶面”(即尺寸长度=5.6cm,宽度=2.5cm的面)上。
条的烧失量(LOI)
条的烧失量(LOI)是通过在小锡箔容器580℃处理来测量的。对于每次测量,首先将锡箔容器在580℃下热处理15分钟以除去所有有机物。使锡箔容器冷却至环境温度,然后称重。四个条(通常在3点弯曲测试中发生断裂之后)被放入锡箔容器并且整体被称重。然后,包含这些条的锡箔容器在580℃下热处理30分钟,使其冷却至环境温度,最后再次称重。然后使用下式计算LOI:
LOI(%)=热处理前条的重量(g)-热处理后的条的重量(g)/热处理之前的条的重量(g)×100%
作为对比例制备的现有技术中的参考粘结剂
粘结剂的示例,参考粘结剂A(脲改性的酚醛树脂,PUF甲阶酚醛树脂)
通过在46%氢氧化钾(25.5g)水溶液的存在下,使37%的甲醛(606g)水溶液和苯酚(189g)水溶液以大约1℃/分钟的加热速率在84℃的反应温度下反应来制备酚醛树脂。在84℃下继续反应,直到树脂的酸耐受性为4,并且大部分苯酚被转化。然后加入尿素(241g)并将混合物冷却。酸耐受性(AT)表示可以用酸稀释给定体积的粘结剂的次数,而不使混合物变成浑浊的(粘结剂沉淀)。硫酸用于确定在粘结剂生产中的停止准则,酸耐受性低于4表示粘结剂反应结束。为了测量AT,用1L离子交换水稀释2.5mL浓硫酸(>99%)来制备滴定剂。然后在室温下用该滴定剂滴定5mL待研究的粘结剂,同时通过手动摇动保持粘结剂;如果优选的话,使用磁力搅拌器和磁力棒。继续滴定,直到在粘结剂中出现轻微的模糊时,当摇动粘结剂时,模糊不消失。
酸耐受性(AT)通过将用于滴定(mL)的酸的量除以样品的量(mL)来计算。
AT=(使用滴定体积(mL))/(样品体积(mL))
使用获得的脲改性酚醛树脂,通过加入25%的氨(90mL)水溶液和硫酸铵(13.2g)水溶液,随后是水(1.30kg)来制备粘结剂。然后如上所述测量粘结剂固体,并且用所需量的水和硅烷(Momentive VS-142)稀释混合物以用于机械强度研究(15%粘结剂固体溶液,0.5%的粘结剂固体硅烷)。
根据本发明的粘结剂
测定根据本发明的粘结剂的以下特性。
试剂
明胶(Speisegelatine,A型,猪,120和180布卢姆;Imagel LB,B型,122布卢姆)是从Gelita AG公司获得。Tannorouge栗树单宁得自布罗兰bvba公司(Brouwland bvba)。琼脂(05039),结冷胶(P8169),来自柑橘皮的果胶(P9135),来自褐藻的海藻酸钠(A0682),羧甲基纤维素钠(419303),可溶性淀粉(S9765),和氢氧化钠购自西格玛奥德里奇公司(Sigma-Aldrich)。为简单起见,这些试剂被认为是完全纯净和无水的。
粘结剂组分固体含量—定义
固化前,给定粘结剂溶液中每种组分的含量基于组分的无水质量。可使用以下公式:
粘结剂组分固体含量(%)=粘结剂组分A固体(g)+粘结剂组分B固体(g)+……/混合物总重量(g)×100%(%)
机械强度研究(条测试)—过程
在条(bar)测试中测试粘结剂的机械强度。对于每种粘结剂,由粘结剂和来自石棉纺丝生产的石棉丸的混合物制造8至16个条。所述丸是与石棉纤维具有相同熔融组合物的颗粒,并且通常被认为是来自纺丝工艺的废产物。用于条状组合物的丸的尺寸为0.25至0.50毫米。
如以下实例中所述获得粘结剂溶液。对于凝结相对较慢的粘结剂,将粘结剂溶液的样品(16.0g用于具有10至15%粘结剂组分固体的粘结剂;32.0g用于具有5%粘结剂组分固体的粘结剂)与丸(80.0g)混合。所得混合物然后被均分到耐热硅树脂形式的四个插槽中以用于制造小条(每种形式4×5个插槽;插槽顶部尺寸:长度=5.6cm,宽度=2.5cm;插槽底部尺寸:长度=5.3cm,宽度=2.2cm;插槽高度=1.1cm)。对于凝结相对较快的粘结剂,粘结剂溶液的样品(8.0g用于具有10至15%粘结剂组分固体的粘结剂和16.0g用于具有5%粘结剂组分固体的粘结剂)与丸(40.0g,使用前预加热到35至40℃)充分混合,所得的混合物然后仅被均分到两个插槽。在每个条的制造过程中,根据需要压制放置在槽中的混合物,然后用塑料刮刀整平以产生均匀的条表面。以此方式制得来自每个粘结剂的8-16个条。然后将所得的条在室温下固化1至2天,或者,首先以表格中列出的温度在炉中固化15小时,随后在室温下固化1至2天。如果在该时间之后仍未充分固化,则在35℃下将条固化1天。然后小心地从容器中取出条,将其倒置,并在室温下保持一天以便完全固化。在高压釜内老化8-16个条中的一半(15分钟/120℃/1.2巴)。
干燥1至2天后,所有的条在3点弯曲测试中发生断裂(测试速度:10.0mm/min;破裂水平:50%;标称强度:30N/mm2;支持距离:40mm;最大挠曲20mm;标称e模块10000N/mm2)在弯曲电车站(Bent Tram machine)上,研究其机械强度。将条放置在机器中的“顶面”(即尺寸长度=5.6cm,宽度=2.5cm的面)上。
条的烧失量(LOI)
条的烧失量(LOI)是通过在小锡箔容器580℃处理来测量的。对于每次测量,首先将锡箔容器在580℃下热处理15分钟以除去所有有机物。使锡箔容器冷却至环境温度,然后称重。四个条(通常在3点弯曲测试中发生断裂之后)被放入锡箔容器并且整体被称重。然后,包含这些条的锡箔容器在580℃下热处理30分钟,使其冷却至环境温度,最后再次称重。然后使用下式计算LOI:
LOI(%)=热处理前条的重量(g)-热处理后的条的重量(g)/热处理之前的条的重量(g)×100%
粘结剂实例,条目1
在50℃下将明胶(Speisegelatine,A型,猪,120布卢姆,7.5g)在水(42.5g)中的混合物搅拌约15至30分钟直至获得澄清溶液(pH5.1)。然后所生成的溶液用于后续实验。
粘结剂实施例,条目3
在50℃下将明胶(Speisegelatine,A型,猪,180布卢姆,8.82g)在水(50.0g)中的混合物搅拌约15至30分钟直至获得澄清溶液(pH5.2)。然后所生成的溶液用于后续实验。
粘结剂实施例,条目5
在50℃下将明胶(Imagel LB,B型,122布卢姆,8.82g)在水(50.0g)中的混合物搅拌约15-30分钟直至获得澄清溶液(pH 5.1)。然后所生成的溶液用于后续实验。
粘结剂实施例,条目7
向85℃下剧烈搅拌的水(50.0g)中经大约15分钟分批加入羧甲基纤维素钠(2.63g)。在85℃下继续搅拌0.5至1h,直到获得澄清溶液(pH 8.4)。然后所生成的溶液用于后续实验。
粘结剂实施例,条目8
向85℃下剧烈搅拌的水(50.0g)中经大约15分钟分批加入可溶性淀粉(2.63g)。在85℃下继续进一步搅拌0.5至1h,直到获得澄清溶液(pH 6.4)。然后所生成的溶液用于后续实验。
粘结剂实施例,条目9
向85℃下剧烈搅拌的水(50.0g)中经大约15分钟分批加入琼脂(2.63g)。在85℃下继续搅拌0.5至1h,直到获得澄清溶液。
在50℃下将明胶(Speisegelatine,A型,猪,120布卢姆,8.82g)在水(50.0g)中的混合物搅拌约15-30分钟直至获得澄清溶液。然后加入上述琼脂溶液的一部分(19.6g,从而有效0.98g琼脂和18.6g水),并且在50℃下继续搅拌5分钟(pH 5.3)。然后所生成的溶液用于后续实验。
粘结剂实施例,条目10
向85℃下剧烈搅拌的水(50.0g)中经大约15分钟分批加入结冷胶(2.63g)。在85℃下继续搅拌0.5至1h,直到获得澄清溶液。
在50℃下将明胶(Speisegelatine,A型,猪,120布卢姆,8.82g)在水(50.0g)中的混合物搅拌约15-30分钟直至获得澄清溶液。然后加入上述结冷胶溶液的一部分(19.6g,从而有效0.98g结冷胶和18.6g水),并且在50℃下继续搅拌5分钟(pH 5.3)。然后所生成的溶液用于后续实验。
粘结剂实施例,条目11
向85℃下剧烈搅拌的水(50.0g)中经大约15分钟分批加入果胶(2.63g)。在85℃下继续搅拌0.5至1h,直到获得澄清溶液。
在50℃下将明胶(Speisegelatine,A型,猪,120布卢姆,8.82g)在水(50.0g)中的混合物搅拌约15-30分钟直至获得澄清溶液。
然后加入上述果胶溶液的一部分(19.6g,从而有效0.98g果胶和18.6g水),并且在50℃下继续搅拌5分钟(pH 4.8)。然后所生成的溶液用于后续实验。
粘结剂实施例,条目12
向85℃下剧烈搅拌的水(50.0g)中经大约15分钟分批加入海藻酸钠(2.63g)。在85℃下继续搅拌0.5至1h,直到获得澄清溶液。
在50℃下将明胶(Speisegelatine,A型,猪,120布卢姆,8.82g)在水(50.0g)中的混合物搅拌约15-30分钟直至获得澄清溶液。然后加入上述海藻酸钠溶液的一部分(19.6g,从而有效0.98g海藻酸钠和18.6g水),并且在50℃下继续搅拌5分钟(pH 5.3)。然后所生成的溶液用于后续实验。
粘结剂实施例,条目13
在室温下搅拌1M NaOH(15.75g),加入栗树单宁(4.50g)。在室温下继续搅拌5至10分钟,得到深红色的棕色溶液。
在50℃下将明胶(Speisegelatine,A型,猪,120布卢姆,8.00g)在水(72.0g)中的混合物搅拌约15至30分钟直至获得澄清溶液(pH4.8)。然后加入1M NaOH(3.50g)(pH 9.3),然后加入上述栗树单宁溶液的一部分(3.60g;从而有效地0.80g栗树单宁)。在50℃下进一步搅拌1至2分钟后,将所得的褐色混合物(pH 9.2)用于后续实验。
粘结剂实施例,条目14
在室温下搅拌1M NaOH(15.75g),加入栗树单宁(4.50g)。在室温下继续搅拌5至10分钟,得到深红色的棕色溶液。
在50℃下将明胶(Speisegelatine,A型,猪,120布卢姆,10.0g)在水(56.7g)中的混合物搅拌约15-30分钟直至获得澄清溶液(pH 4.9)。然后加入1M NaOH(4.00g)(pH 9.1),然后加入上述栗树单宁溶液的一部分(4.50g;因此有效量为1.00g栗树单宁)。在50℃下进一步搅拌1至2分钟后,将所得的褐色混合物(pH 9.1)用于后续实验。
粘结剂实施例,条目17
在室温下搅拌1M NaOH(15.75g),加入栗树单宁(4.50g)。在室温下继续搅拌5至10分钟,得到深红色的棕色溶液。
在50℃下将明胶(Speisegelatine,A型,猪,180布卢姆,10.0g)在水(56.7g)中的混合物搅拌约15至30分钟直至获得澄清溶液(pH4.8)。然后加入1M NaOH(3.50g)(pH 9.2),然后加入上述栗树单宁溶液的一部分(4.50g;因此有效量为1.00g栗树单宁)。在50℃下进一步搅拌1至2分钟后,将所得的褐色混合物(pH 9.2)用于后续实验。
粘结剂实施例,条目19
在室温下搅拌1M NaOH(15.75g),加入栗树单宁(4.50g)。在室温下继续搅拌5至10分钟,得到深红色的棕色溶液。
在50℃下将明胶(Imagel LB,B型,122布卢姆,10.0g)在水(56.7g)中的混合物搅拌约15至30分钟直至获得澄清溶液(pH 4.7)。然后加入1M NaOH(3.50g)(pH 9.2),然后加入上述栗树单宁溶液的一部分(4.50g;因此有效量为1.00g栗树单宁)。在50℃下进一步搅拌1至2分钟后,将所得的褐色混合物(pH 9.2)用于后续实验。
粘结剂实施例,条目21
向85℃下剧烈搅拌的水(50.0g)中经大约15分钟分批加入琼脂(2.63g)。在85℃下继续搅拌0.5至1h,直到获得澄清溶液。
在室温下搅拌1M NaOH(15.75g),加入栗树单宁(4.50g)。在室温下继续搅拌5至10分钟,得到深红色的棕色溶液。
在50℃下将明胶(Speisegelatine,A型,猪,120布卢姆,10.0g)在水(56.7g)中的混合物搅拌约15至30分钟直至获得澄清溶液(pH4.6)。然后加入1M NaOH(4.00g)(pH 9.1),然后加入上述栗树单宁溶液的一部分(4.50g;从而有效地1.00g栗树单宁),然后加入一部分上述琼脂溶液(20.0g;从而有效地1.00g琼脂)。在50℃下进一步搅拌1至2分钟后,将所得的褐色混合物(pH 8.8)用于后续实验。
粘结剂实施例,条目22
向85℃下剧烈搅拌的水(50.0g)中经大约15分钟分批加入果胶(2.63g)。在85℃下继续搅拌0.5至1h,直到获得澄清溶液。
在室温下搅拌1M NaOH(15.75g),加入栗树单宁(4.50g)。在室温下继续搅拌5至10分钟,得到深红色的棕色溶液。
在50℃下将明胶(Speisegelatine,A型,猪,120布卢姆,10.0g)在水(56.7g)中的混合物搅拌约15至30分钟直至获得澄清溶液(pH4.6)。然后加入1M NaOH(4.50g)(pH 9.6),然后加入上述栗树单宁溶液的一部分(4.50g;从而有效地1.00g栗树单宁),然后加入一部分上述果胶溶液(20.0g;从而有效地1.00g果胶)。在50℃下进一步搅拌1至2分钟后,将所得的褐色混合物(pH 8.9)用于后续实验。
粘结剂实施例,条目23
向85℃下剧烈搅拌的水(50.0g)中经大约15分钟分批加入海藻酸钠(2.63g)。在85℃下继续搅拌0.5至1h,直到获得澄清溶液。
在室温下搅拌1M NaOH(15.75g),加入栗树单宁(4.50g)。在室温下继续搅拌5至10分钟,得到深红色的棕色溶液。
在50℃下将明胶(Speisegelatine,A型,猪,120布卢姆,10.0g)在水(56.7g)中的混合物搅拌约15至30分钟直至获得澄清溶液(pH4.6)。然后加入1M NaOH(4.00g)(pH 9.2),然后加入上述栗树单宁溶液的一部分(4.50g;从而有效地1.00g栗树单宁),然后加入一部分上述海藻酸钠溶液(20.0g;从而有效地1.00g海藻酸钠)。在50℃下进一步搅拌1至2分钟后,将所得的褐色混合物(pH 9.0)用于后续实验。
粘结剂实施例,条目24
向85℃下剧烈搅拌的水(50.0g)中经大约15分钟分批加入可溶性淀粉(2.63g)。在85℃下继续搅拌0.5至1h,直到获得澄清溶液。
在室温下搅拌1M NaOH(15.75g),加入栗树单宁(4.50g)。在室温下继续搅拌5至10分钟,得到深红色的棕色溶液。
在50℃下将明胶(Speisegelatine,A型,猪,120布卢姆,10.0g)在水(56.7g)中的混合物搅拌约15至30分钟直至获得澄清溶液(pH4.8)。然后加入1M NaOH(4.00g)(pH 9.1),然后加入上述栗树单宁溶液的一部分(4.50g;从而有效地1.00g栗树单宁),然后加入一部分上述可溶性淀粉溶液(20.0g;从而有效地1.00g可溶性淀粉)。在50℃下进一步搅拌1至2分钟后,将所得的褐色混合物(pH 8.8)用于后续实验。
表1-1:参考粘结剂
| 实例 | A |
| 粘结剂特性 | |
| 粘结剂固体(%) | 15.0 |
| 反应损失(%) | 28.5 |
| pH值 | 9.6 |
| 条固化条件 | |
| 温度(℃/1h) | 200 |
| 条特性 | |
| 机械强度,未老化(kN) | 0.39 |
| 机械强度,老化(kN) | 0.28 |
| LOI,未老化(%) | 2.8 |
表1至表2:各种水胶体
[a]水胶体。[b]水胶体+交联剂。
表1至表3:各种水胶体和交联剂
[a]水胶体。[b]水胶体+交联剂
如从比较表1.1中的结果与表1.2和表1.3中的结果可以看出,用于本发明的粘结剂组合物需要较低的固化温度。参考粘结剂组合物需要200℃的固化温度,而粘结剂1至24在55℃和更低的温度下固化,通常在环境温度下固化。这意味着本发明的粘结剂组合物能够在现场固化或在制造或加工阶段固化。
Claims (22)
1.一种为结构提供隔热和/或隔音的方法,包括以下步骤:
-提供基底,所述基底包括纤维;
-将所述基底施加到所述结构;
-在将所述基底施加到所述结构之前、期间或之后将所述基底与粘结剂组合物共混;
-在所述基底和所述粘结剂组合物已被施加到所述结构之后允许所述粘结剂组合物固化;
其中所述粘结剂组合物包含至少一种水胶体,其中所述至少一种水胶体是动物来源的蛋白质,包括胶原、明胶和水解明胶;
并且其中所述粘结剂组合物包括
至少一种含酚的化合物,诸如选自单宁酸、缩合单宁(原花青素)、可水解单宁、没食子单宁、鞣花单宁、复合单宁中的一种或多种组分的单宁,和/或源自橡树、栗树、火炬树和大穗杯花中的一种或多种的单宁,
和/或
至少一种酶,所述至少一种酶选自转谷氨酰胺酶(EC 2.3.2.13)、蛋白质二硫键异构酶(EC 5.3.4.1)、硫醇氧化酶(EC 1.8.3.2)、多酚氧化酶(EC 1.14.18.1),特别是儿茶酚氧化酶、酪氨酸氧化酶和酚氧化酶、赖氨酰氧化酶(EC 1.4.3.13)和过氧化物酶(EC 1.11.1.7)。
2.根据权利要求1所述的方法,其中所述基底不包含矿棉。
3.根据权利要求1所述的方法,其中所述基底包含纤维,所述纤维为矿物纤维。
4.根据前述权利要求中任一项所述的方法,其中所述基底还包含颗粒材料。
5.根据权利要求4所述的方法,其中所述基底包含颗粒材料,所述颗粒材料选自气凝胶、珍珠岩、蛭石、锡石、相变材料、微球和阻燃剂。
6.根据前述权利要求中任一项所述的方法,其中所述纤维在所述基底与所述粘结剂组合物共混之前不包含任何粘结剂组合物。
7.根据权利要求1至5中任一项所述的方法,其中所述纤维为用固化的粘结剂组合物粘结的纤维的颗粒屑形式。
8.根据前述权利要求中任一项所述的方法,其中所述结构为建筑物或建筑物部件的墙壁、空腔壁、天花板、地板、阁楼或屋顶中的任一者。
9.根据前述权利要求中任一项所述的方法,其中将所述基底与所述粘结剂组合物共混的步骤在将所述基底施加到所述结构期间,通过将所述基底和所述粘结剂组合物同时施加到所述结构而发生。
10.根据权利要求9所述的方法,其中所述基底和所述粘结剂组合物通过喷涂同时施加。
11.根据前述权利要求中任一项所述的方法,其中所述粘结剂组合物的固化在5℃至95℃,诸如5℃至80℃、诸如8℃至50℃、诸如10℃至40℃的温度下发生。
12.根据权利要求1至10中任一项所述的方法,其中所述粘结剂组合物的固化在环境温度下发生。
13.根据前述权利要求中任一项所述的方法,其中将所述基底与所述粘结剂组合物共混的步骤发生在将所述基底施加到所述结构之前不超过20分钟,优选不超过10分钟,最优选不超过5分钟。
14.根据前述权利要求中任一项所述的方法,其中所述粘结剂组合物包含至少两种水胶体,其中一种水胶体为明胶,并且所述至少一种其他水胶体选自果胶、淀粉、藻酸盐、琼脂、卡拉胶、结冷胶、瓜尔胶、阿拉伯树胶、刺槐豆胶、黄原胶、纤维素衍生物诸如羧甲基纤维素、阿拉伯木聚糖、纤维素、凝胶多糖、β-葡聚糖。
15.根据权利要求14所述的方法,其中所述明胶基于所述水胶体的重量计,以10重量%至95重量%,诸如20重量%至80重量%、诸如30重量%至70重量%、诸如40重量%至60重量%的量存在于所述粘结剂组合物中。
16.根据前述权利要求中任一项所述的方法,其中所述粘结剂组合物不是热固性粘结剂。
17.根据前述权利要求中任一项所述的方法,其中所述粘结剂组合物是无甲醛的。
18.根据前述权利要求中任一项所述的方法,其中所述粘结剂组合物基本上由下述物质组成:
至少一种水胶体;
任选地至少一种油;
任选地至少一种pH调节剂;
任选地至少一种交联剂;
任选地至少一种防污剂;
任选地至少一种抗溶胀剂;
水。
19.根据前述权利要求中任一项所述的方法,其中所述固化过程包括干燥过程,特别是通过吹空气或气体越过/穿过所述基底或通过升高温度。
20.一种可通过根据前述权利要求中任一项所述的方法获得的隔离结构。
21.根据权利要求20所述的隔离结构,所述隔离结构为建筑物或建筑物部件的墙壁、空腔壁、天花板、地板、阁楼或屋顶中的任一者。
22.根据权利要求20或21所述的隔离结构,其中由粘结剂粘结的基底块的烧失量(LOI)按重量计,在0.1%至25.0%,诸如0.3%至18.0%、诸如0.5%至12.0%、诸如0.7%至8.0%的范围内。
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