CN110809618A - 矿棉粘结剂 - Google Patents
矿棉粘结剂 Download PDFInfo
- Publication number
- CN110809618A CN110809618A CN201780090636.1A CN201780090636A CN110809618A CN 110809618 A CN110809618 A CN 110809618A CN 201780090636 A CN201780090636 A CN 201780090636A CN 110809618 A CN110809618 A CN 110809618A
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- binder
- binder composition
- oil
- mineral
- mineral fibres
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Classifications
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
本发明涉及一种用于矿物纤维的无甲醛粘结剂组合物,其包含:至少一种含酚和/或醌的化合物,至少一种蛋白质,至少一种脂肪酸甘油酯。
Description
技术领域
本发明涉及矿棉粘结剂、用所述粘结剂生产矿棉产品的方法以及用所述粘结剂制成的矿棉产品。
背景技术
矿物纤维产品通常包括人造玻璃状纤维(MMVF),诸如玻璃纤维、陶瓷纤维、玄武岩纤维、渣棉、矿棉和石棉(岩棉),它们通过固化的热固性聚合物粘结剂材料粘结在一起。用作隔热或隔音产品的粘结矿物纤维垫通常是以常规方式,例如通过纺杯法或级联转子法,将适当原材料制得的熔体转换为纤维来生产。将纤维吹入成形室,气载的纤维趁热用粘结剂溶液喷涂,并在行进输送机上随机沉积为垫或网。然后将纤维垫转移到固化炉中,其中将加热的空气吹入垫以固化粘结剂并将矿物纤维牢固地粘结在一起。
过去,所选择的粘结剂树脂为苯酚-甲醛树脂,其可经济地生产,并且可在用作粘结剂之前用脲类扩展(extend)。然而,涉及降低或消除甲醛排放的现有和拟议立法导致了无甲醛粘结剂的发展,例如,基于聚羧基聚合物和多元醇或多胺的粘结剂组合物,诸如EP-A-583086、EP-A-990727、EP-A-1741726、US-A-5,318,990和US-A-2007/0173588所公开的。
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,需要不断地提供能经济地生产的无甲醛粘结剂。
与先前已知的来自矿物纤维的含水粘结剂组合物有关的另一个效果是,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矿棉粘结剂。
与先前已知的用于矿物纤维的含水粘结剂组合物有关的另一个效果是,其包含腐蚀性和/或有害的组分。这需要给矿棉制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/或有害材料的用于矿物纤维的粘结剂组合物。
与先前已知的来自矿物纤维的含水粘结剂组合物有关的再一个效果是,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。炉为几米长,以容纳连续进料到炉中的网(web),并且确保在离开炉时网被完全固化。此类炉设备与大量的能耗相关联。
参考文献C.K.de la Caba,A.Eceiza,R.Ruseckaite,I.Mondragon inBiores.Technol.2010,101,6836-6842涉及由来自植物和肉类工业废料的可再生原料替换不可生物降解的塑料薄膜。就此而论,该参考文献描述了在明胶的改性中使用可水解栗树单宁,以形成膜。该参考文献没有描述粘结剂,特别是用于矿棉的粘结剂。
以前已经提出了基于可再生材料的矿棉粘结剂。尽管这些粘结剂中的一些显示出优异的总体性能,但是与用苯酚-甲醛树脂制得的矿棉产品相比,用这些粘结剂制得的矿棉产品在强度和吸水率方面仍存在一些缺点。
发明内容
因此,本发明的目的是提供一种粘结剂组合物,其尤其适用于粘结矿物纤维,使用可再生材料作为原料,减少或消除腐蚀性和/或有害的材料,并且同时允许制备具有优异的强度性能和低吸水率的矿棉产品。
此外,本发明的目的是提供一种粘结剂组合物,其不需要高温以进行固化,因此不需要在用粘结剂组合物粘结的产品的生产中应用高温。
本发明的另一个目的是提供一种用这种粘结剂组合物粘结的矿棉制品。
本发明的另一个目的是提供一种制造这种矿棉产品的方法。
本发明的另一个目的是提供这种粘结剂组合物用于制备矿棉产品的用途。
根据本发明的第一方面,提供了一种用于矿物纤维的优选无甲醛的粘结剂组合物,其包含:
-至少一种含酚和/或醌的化合物,
-至少一种蛋白质,
-至少一种脂肪酸甘油酯。
根据本发明的第二方面,提供了一种矿棉产品,其包含由粘结剂粘结的矿物纤维,该粘结剂由这种粘结剂组合物的固化得到。
根据本发明的第三方面,提供了一种用于生产矿棉产品的方法,其包括将矿物纤维与这种粘结剂组合物接触的步骤。
根据本发明的第四方面,提供了这种粘结剂组合物用于制备矿棉产品的用途。
本发明人惊奇地发现,可获得一种具有优异的强度性质和低吸水率的矿棉制品,其包含由粘结剂粘结的矿物纤维,该粘结剂由粘结剂组合物的固化得到,其中粘结剂组合物很大程度上可由可再生材料生产,不包含或仅在很小程度上包含任何腐蚀性和/或有害试剂,并且矿棉制品的制备不会导致在制备期间造成诸如VOC(挥发性有机化合物)的污染。
具体实施方式
根据本发明的粘结剂组合物包含:
-至少一种含酚和/或醌的化合物,
-至少一种蛋白质,
-至少一种脂肪酸甘油酯。
在一个优选的实施方案中,根据本发明的粘结剂是无甲醛的。
为了本专利申请的目的,术语“无甲醛”被定义为表征矿棉产品,其中来自矿棉产品的甲醛的排放低于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ISO16000进行测试。
根据本发明的矿棉产品的实施方案的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之后矿棉产品失去其一部分强度时,根据本发明的矿棉产品可以重新获得一部分原始强度。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,根据本发明的矿棉产品中的这种惊人特性是由于在由含酚和/或醌的化合物交联的蛋白质的网络中形成键的复杂性质引起的,其还包括四级结构和氢键,并且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。
粘结剂的含酚和/或醌的化合物组分
根据本发明的粘结剂组合物包含粘结剂的含酚和/或醌的化合物组分,特别是一种或多种酚类化合物和/或一种或多种醌。
酚类化合物或酚类是具有一个或多个直接附接到芳环上的羟基的化合物。多酚(或多羟基酚)是具有一个以上附接到一个或多个芳环的酚羟基的化合物。酚类化合物是植物的特征,并且它们通常作为组群以酯类或糖苷类而不是游离化合物被发现。
术语“酚类”涵盖一组非常庞大且多样的化学化合物。优选地,含酚化合物是根据基于分子中的碳数量的方案的化合物,如W.Vermerris、R.Nicholson在“PhenolicCompound Biochemistry,Springer Netherlands,2008”中所详述。
优选地,含酚化合物为选自由以下构成的组中的一种或多种组分的形式:具有C6结构的化合物,诸如简单的酚类,诸如间苯二酚、间苯三酚;诸如具有C6-C1结构的化合物,诸如羟基苯甲酸,诸如对羟基苯甲酸、没食子酸、原儿茶酸、水杨酸、香草酸,诸如羟基苯甲醛,诸如香草醛;诸如具有C6-C2结构的化合物,诸如羟基苯乙酮,诸如2-羟基苯乙酮,诸如羟基苯乙酸,诸如2-羟基苯乙酸;诸如具有C6-C3结构的化合物,诸如肉桂酸,诸如对香豆酸、咖啡酸、阿魏酸、5-羟基阿魏酸、芥子酸,诸如肉桂酸酯,诸如绿原酸、芥子酰苹果酸酯、芥子酰胆碱,诸如肉桂醛,诸如肉桂醇,诸如香豆素,诸如伞形酮、4-甲基伞形酮,诸如异香豆素,诸如岩白菜素,诸如色酮;诸如具有C15结构的化合物,诸如黄酮类,诸如黄烷酮、异黄酮、异黄烷酮、新型黄酮类,诸如查尔酮,诸如紫铆因,诸如二氢查耳酮,诸如根皮苷,诸如橙酮,诸如黄烷酮类,诸如柚皮素,诸如二氢黄酮醇类,诸如花旗松素,诸如黄烷类,诸如无色花色素,诸如无色花青素、无色翠雀定,诸如黄烷-3-醇,诸如儿茶素、没食子儿茶素,诸如黄酮类,诸如山奈酚、槲皮素、杨梅素,诸如花青素,诸如花葵素、花青色素、芍药色素、飞燕草色素、牵牛花色素、锦葵色素,诸如脱氧花青素,诸如芹菜定、木犀草定、7-甲氧基芹菜定、5-甲氧基-木犀草定,诸如花色素苷,诸如矮牵牛花色素;诸如具有C30结构的化合物,诸如双黄酮类,诸如银杏黄素;诸如具有C6-C1-C6结构的化合物,诸如苯甲酮,诸如氧杂蒽酮;诸如具有C6-C2-C6结构的化合物,诸如芪类,诸如白藜芦醇、银松素;诸如具有C6/C10/C14结构的化合物,诸如苯醌,诸如萘醌,诸如胡桃醌,诸如蒽醌,诸如大黄素;诸如具有顺式结构的化合物,诸如甜菜红素,诸如甜菜素,诸如多酚和/或多羟基酚,诸如木脂素、新木脂素(由偶联单木质醇诸如对香豆醇、松柏醇和芥子醇得到的二聚物或低聚物),诸如松脂醇、芝麻素、大侧柏酸,诸如木质素(主要由单木质醇前体对香豆醇、松柏醇和芥子醇合成),诸如单宁,例如缩合单宁(原花青素),诸如原花青素B2,诸如可水解单宁,诸如没食子单宁,诸如鞣花单宁,诸如复合单宁,诸如acutissimin A,诸如单宁酸,诸如鞣红。
在一个优选的实施方案中,含酚化合物选自简单的酚类、具有比C6结构更复杂的结构的含酚化合物,诸如简单的酚类、多酚和/或多羟基酚的低聚物。
醌是芳族化合物的氧化衍生物,并且通常易于由具有供电子取代基的反应性芳族化合物诸如酚类制成。可用于本发明的醌包括苯醌、萘醌、蒽醌和指甲花醌。
根据本发明的含酚和/或醌的化合物也可以是含酚、多酚和/或醌的合成或半合成分子或构建体。此类构建体的示例为用含酚和/或醌的侧链改性的蛋白质、肽、类肽(诸如,N-取代的甘氨酸、N-取代的β-丙氨酸的线性和/或环状低聚物和/或聚合物)、芳基类肽(诸如,N-取代的氨甲基苯甲酰胺的线性和/或环状低聚物和/或聚合物)、聚苯乙烯。用含酚和/或醌的侧链修饰的树形分子是另一个示例。
单宁包含一组在结构上具有广泛多样性的化合物,这些化合物都具有结合和沉淀蛋白质的能力。单宁在许多不同的植物物种中都很丰富,特别是橡树、栗树、鹿角漆树和大穗杯花。单宁可存在于叶子、树皮和果实中。单宁可分为三组:缩合单宁、可水解单宁和复合单宁。缩合单宁或原花青素是由黄烷-3-醇(儿茶素)单元组成的低聚或聚合类黄酮。没食子单宁是可水解单宁,其中多元醇核心被10至12个没食子酸残基取代。没食子单宁中最常见的多元醇是D-葡萄糖,但是一些没食子单宁含有儿茶素和三萜单元作为核心多元醇。鞣花单宁是不同于没食子单宁的可水解单宁,因为它们在相邻的没食子酰基部分之间含有额外的C-C键。复合单宁被定义为其中儿茶素单元与没食子单宁或鞣花单宁单元糖苷化地结合的单宁。
本发明人惊奇地发现,可以使用各种这种含酚和/或醌的化合物来交联蛋白质,然后形成粘结剂组合物。通常,这些含酚和/或醌的化合物组分从植物组织中获得,因此是可再生材料。在一些实施方案中,这些化合物也是无毒的和无腐蚀性的。作为另一个优点,这些化合物是抗菌的,因此将其抗菌特性赋予由这种粘结剂粘结的矿棉产品。
在一个优选的实施方案中,含酚和/或醌的化合物选自单宁酸、鞣花单宁和没食子单宁中的一种或多种组分,其中单宁源自橡木、栗子、鹿角漆树和大穗杯花中的一者或多者。
粘结剂的蛋白质组分
优选地,粘结剂的蛋白质组分为选自由以下构成的组中的一种或多种蛋白质的形式:来自动物来源的蛋白质,包括胶原、明胶、水解明胶和来自牛奶、鸡蛋中的蛋白质(酪蛋白、乳清);来自植物来源的蛋白质,包括来自豆类、谷物、全谷类、坚果、种子和水果中的蛋白质,如来自荞麦、燕麦、黑麦、小米、玉蜀黍(玉米)、大米、小麦、碾碎干小麦、高粱、苋属植物、藜麦、大豆的蛋白质(大豆蛋白)、扁豆、芸豆、白豆、绿豆、鹰嘴豆、豇豆、利马豆、木豆、羽扇豆、翼豆、杏仁、巴西坚果、腰果、碧根果、核桃、棉籽、南瓜籽、大麻籽、芝麻籽和向日葵籽;多酚蛋白质,诸如贻贝足丝蛋白质。
胶原是活体组织中非常丰富的物质:胶原是结缔组织中的主要组分并且占哺乳动物中总蛋白质含量的25%至35%。明胶来源于胶原的化学降解。明胶也可通过重组技术产生。明胶为水溶性的,并且具有10.000g/mol至500.000g/mol,诸如30.000g/mol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,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条α1(I)和一条α2(I)链组成。
明胶溶液可经历卷曲螺旋转变。
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。在一个实施方案中,转谷氨酰胺酶用于将赖氨酸与谷氨酰胺残基连接;在一个实施方案中,戊二醛用于将赖氨酸与赖氨酸连接,在一个实施方案中,单宁用于连接赖氨酸残基。
明胶还可进一步水解成小至3000g/mol的较小片段。
在冷却明胶溶液时,可形成胶原样螺旋。
明胶可形成螺旋结构。
在一个实施方案中,包含蛋白质的固化粘结剂包括螺旋结构。
在一个实施方案中,该至少一种蛋白质为低强度明胶,诸如具有30至125布卢姆(Bloom)凝胶强度的明胶。
在一个实施方案中,该至少一种蛋白质为中等强度明胶,诸如具有125至180布卢姆凝胶强度的明胶。
在一个实施方案中,该至少一种蛋白质为高强度明胶,诸如具有180至300布卢姆凝胶强度的明胶。
在一个优选的实施方案中,明胶优选来自哺乳动物、鸟类,诸如来自牛、猪、马、家禽和/或来自鱼鳞、鱼皮中的一种或多种来源。
在一个实施方案中,尿素可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,这在一些实施方案中可能是合意的。尿素的添加也会导致产品的软化。
本发明人已发现,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,在一些实施方案中,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,本发明人认为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,在一些实施方案中,固化粘结剂可经受得住高达300℃的温度而不降解。
脂肪酸甘油酯
根据本发明的粘结剂组合物包含至少一种脂肪酸甘油酯形式的组分。
脂肪酸为具有饱和的或不饱和的脂族链的羧酸。
甘油为IUPAC名称为丙烷-1,2,3-三醇的多元醇化合物。
天然存在的油脂是与脂肪酸的甘油酯(也称为甘油三酸酯)。
为了本发明的目的,术语脂肪酸甘油酯是指甘油与脂肪酸的单酯、二酯和三酯。
尽管术语脂肪酸在本发明的上下文中可为具有脂族链的任何羧酸,但是优选地其是具有含4至28个碳原子,优选地偶数个碳原子的脂族链的羧酸。优选地,脂肪酸的脂族链是直链的。
在一个优选的实施方案中,至少一种脂肪酸甘油酯为植物油和/或动物油的形式。在本发明的上下文中,术语“油”包括油或脂肪形式的至少一种脂肪酸甘油酯。
在一个优选的实施方案中,至少一种脂肪酸甘油酯是基于植物的油。
在一个优选的实施方案中,至少一种脂肪酸甘油酯为果肉脂肪形式,诸如棕榈油、橄榄油、鳄梨油;种仁脂肪,诸如月桂酸油,诸如椰子油、棕榈仁油、巴巴苏油和其他棕榈籽油、其他来源的月桂酸油;棕榈-硬脂酸油,诸如可可油、牛油树脂、婆罗洲脂和相关脂肪(植物黄油);棕榈酸油,诸如棉籽油、木棉及相关油、南瓜籽油、玉米(玉蜀黍)油、谷物油;油酸-亚麻酸油,诸如向日葵油、芝麻油、亚麻籽油、紫苏油、大麻籽油、茶籽油、红花和尼日尔籽油、葡萄籽油、罂粟籽油、豆科植物油,诸如大豆油、花生油、羽扇豆油;十字花科油,诸如油菜籽油、芥菜籽油;共轭酸油,诸如桐油和相关油、奥蒂油和相关油;取代的脂肪酸油,诸如蓖麻油、大风子(chaulmoogra\hydnocarpus\gorli)油、斑鸠菊油;动物脂肪,诸如陆生动物脂肪,如猪油、牛脂、羊脂、马脂、鹅脂、鸡脂;海洋油,诸如鲸油和鱼油。
在一个优选的实施方案中,至少一种脂肪酸甘油酯为植物油的形式,特别是选自亚麻籽油、橄榄油、桐油、椰子油、大麻油、油菜籽油和向日葵油中的一种或多种组分。
在一个优选的实施方案中,至少一种脂肪酸甘油酯选自由以下构成的组的一种或多种组分:具有在约136至178范围内的碘值的植物油,诸如具有在约136至178的范围内的碘值的亚麻子油;具有在约80至88的范围内的碘值的植物油,诸如具有在约80至88的范围内的碘值的橄榄油;具有在约163至173的范围内的碘值的植物油,诸如具有在约163至173的范围内的碘值的桐油;具有在约7至10的范围内的碘值的植物油,诸如具有在约7至10的范围内的碘值的椰子油;具有在约140至170的范围内的碘值的植物油,诸如具有在约140至170的范围内的碘值的大麻油;具有在约94至120的范围内的碘值的植物油,诸如具有在约94至120的范围内的碘值的油菜籽油;具有在约118至144的范围内的碘值的植物油,诸如具有在约118至144的范围内的碘值的向日葵油。
在一个实施方案中,至少一种脂肪酸甘油酯不是天然来源的。
在一个实施方案中,至少一种脂肪酸甘油酯是改性的植物或动物油。
在一个实施方案中,至少一种脂肪酸甘油酯包含至少一种反式脂肪酸。
在一个替代的优选的实施方案中,至少一种脂肪酸甘油酯为动物油诸如鱼油的形式。
在一个实施方案中,粘结剂由包含明胶的粘结剂组合物的固化得到,并且其中粘结剂组合物还包含单宁,其选自:由单宁酸、缩合单宁(原花青素)、可水解单宁、没食子单宁、鞣花单宁、复合单宁和/或源自橡木、栗子、鹿角漆树和大穗杯花中的单宁构成的组中的一种或多种组分,优选地单宁酸,并且粘结剂组合物还包含至少一种脂肪酸甘油酯,诸如选自由亚麻籽油、橄榄油、桐油、椰子油、大麻油、油菜籽油和向日葵油构成的组中的一种或多种组分的至少一种脂肪酸甘油酯。
本发明人已经发现,根据本发明的粘结剂中使用的脂肪酸甘油酯的脂肪酸不饱和量的参数可用来区分优选的实施方案。脂肪酸中的不饱和量通常通过碘值(也称为碘价或吸碘值或碘指数)来测量。碘值越高,脂肪酸中存在的C=C键越多。为了确定碘值作为脂肪酸不饱和度的量度,我们参考了Thomas,Alfred(2012)“Fats and fatty oils”inUllmann's Encyclopedia of industrial chemistry,Weinheim,Wiley-VCH。
在一个优选的实施方案中,至少一种脂肪酸甘油酯包含具有碘值为≥75,诸如75至180、诸如≥130、诸如130至180的植物油和/或动物油。
在一个替代的优选的实施方案中,至少一种脂肪酸甘油酯包括碘值为≤100,诸如≤25的植物油和/或动物油。
在一个实施方案中,至少一种脂肪酸甘油酯是干性油。对于干性油的定义,请参见Poth,Ulrich(2012)“Drying oils and related products”in Ullmann's Encyclopediaof industrial chemistry,Weinheim,Wiley-VCH。
因此,本发明人已经发现,当碘值在相当高的范围内或可替代地在相当低的范围内时,可获得特别好的结果。尽管不希望受到任何特定理论的束缚,但本发明人认为,一方面高碘值而另一方面低碘值的脂肪酸酯所赋予的有利性质基于不同的机理。本发明人认为,具有高碘值的脂肪酸的甘油酯的有利性质可能是由于在这些脂肪酸中大量存在的C=C双键参与了交联反应,而具有低碘值且缺乏大量C=C双键的脂肪酸的甘油酯可能允许范德华相互作用稳定固化的粘结剂。本发明人认为脂肪酸甘油酯的极性端与至少一种蛋白质的极性区域相互作用,而非极性端与至少一种蛋白质的非极性区域相互作用。
粘结剂组分的反应
不想受任何特定理论的束缚,本发明人认为含酚和/或醌的化合物与蛋白质之间的反应至少部分依赖于酚到醌的氧化,然后是来自蛋白质的胺和/或硫醇基的亲核攻击,这导致含酚和/或醌的化合物交联蛋白质。
在一个优选的实施方案中,根据本发明的粘结剂组合物中含酚和/或醌的化合物的含量基于蛋白质干重计为1至70重量%,诸如2至60重量%,诸如3至50重量%,诸如4至40重量%,诸如5至35重量%。
在一个替代的优选实施方案中,蛋白质中的(赖氨酸+半胱氨酸)与含酚和/或醌的化合物中的(酚+醌)的质量比为1:5.78至1:0.08,诸如1:2.89至1:0.09、诸如1:1.93至1:0.12、诸如1:1.45至1:0.15、诸如1:1.16至1:0.17。
术语“蛋白质中的(赖氨酸+半胱氨酸)与含苯酚和/或醌的化合物中的(酚+醌)的质量比”应理解为蛋白质组分中赖氨酸+半胱氨酸残基的总质量与含酚和/或醌的化合物中酚+醌残基的总质量之比。
在一个优选的实施方案中,脂肪酸甘油酯的含量基于蛋白质干重计为0.5重量%至40重量%,诸如1重量%至30重量%,诸如1.5重量%至20重量%,诸如3重量%至10重量%,诸如4重量%至7.5重量%。
本发明人已发现,粘结剂的固化在碱性条件下强烈加快。因此,在一个实施方案中,用于矿物纤维的粘结剂组合物包含pH调节剂,该pH调节剂优选为碱、诸如有机碱、诸如胺、或其盐,无机碱、诸如金属氢氧化物、诸如KOH或NaOH、氨或其盐的形式。
在一个特定的优选实施方案中,pH调节剂为碱金属氢氧化物,特别是NaOH。
在一个优选的实施方案中,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。
在一个实施方案中,蛋白质包含多酚蛋白质。
这些蛋白质包括高水平的酪氨酸的翻译后修饰—氧化—形式,L-3,4-二羟基苯丙氨酸(左旋多巴,L-DOPA)。还可参见J.J.Wilker Nature Chem.Biol.2011,7,579-580以了解这些蛋白质。
添加剂
在一个实施方案中,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(Chitosan)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(nisin)。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(lemon grass)或肉桂油。
在一个优选的实施方案中,根据本发明的粘结剂组合物含有添加剂。
其他添加剂可以是诸如一种或多种反应性或非反应性有机硅的组分,并且可将其加入粘结剂中。优选地,一种或多种反应性或非反应性有机硅选自如下有机硅:该有机硅的主链由有机硅氧烷残基,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,其具有至少一个羟基、酰基、羧基或酸酐、胺、环氧基或乙烯基官能团,该官能团能够与粘结剂组合物的至少一种组分反应,并且优选的是,该有机硅以粘结剂的总质量计,以0.1重量%至15重量%,优选地0.1重量%至10重量%,更优选地0.3重量%至8重量%的量存在。
在一个实施方案中,可将乳化的烃油加入粘结剂中。
如上已经描述,许多含酚和/或醌的化合物,特别是多酚,具有抗菌特性,因此将抗菌性质赋予粘结剂。然而,在一个实施方案中,可将防污剂加入粘结剂组合物中。
在一个实施方案中,可将抗溶胀剂诸如单宁酸和/或单宁加入粘结剂中。
在一个实施方案中,根据本发明的粘结剂组合物包含胺接头和/或硫醇/硫醇盐接头形式的添加剂。这些胺接头和/或硫醇/硫醇盐接头形式的添加剂在通过醌-胺和/或醌-硫醇途径进行粘结剂的交联反应时是特别有用的。
在一个实施方案中,根据本发明的粘结剂组合物包含含有金属离子诸如铁离子的添加剂。
上面讨论的多酚蛋白质诸如贻贝粘附蛋白依赖于3,4-二羟基苯基部分来增强表面粘附。这与所选类型的阳离子诸如铁离子的分泌相结合来实现。在一个实施方案中,可以说粘结剂模仿多酚蛋白质,因此添加各种阳离子可以改善粘结剂特性。当这些有利离子与含水粘结剂接触时,也可以从矿物纤维表面释放出来。
在一个实施方案中,矿棉产品包含岩棉。不受理论的束缚,据信某些离子从玻璃状纤维浸出可有助于粘结强度。这种机制可能类似于贻贝粘附蛋白获得表面粘附的机制。这与所选类型的阳离子诸如铁离子的分泌相结合来实现。
在一个实施方案中,根据本发明的粘结剂组合物含有选自PEG型试剂、硅烷和羟基磷灰石的添加剂形式的其他添加剂。
氧化剂作为添加剂可用于增加酚类的氧化速率。一个示例是酪氨酸酶,其将酚氧化成羟基酚/醌,因此加速了粘结剂形成反应。
在另一个实施方案中,氧化剂是提供给粘结剂的氧气。
在一个实施方案中,固化在富氧环境中进行。
包含由粘结剂粘结的矿棉纤维的矿棉产品
本发明还涉及由粘结剂粘结的矿棉产品,该粘结剂由所述粘结剂组合物的固化得到。
在一个优选的实施方案中,矿棉产品的密度在10kg/m3至1200kg/m3,诸如30kg/m3至800kg/m3、诸如40kg/m3至600kg/m3、诸如50kg/m3至250kg/m3、诸如60kg/m3至200kg/m3的范围内。
在一个优选的实施方案中,根据本发明的矿棉产品为隔热产品,特别是具有10kg/m3至200kg/m3的密度。
在一个替代的实施方案中,根据本发明的矿棉产品为外墙面板,特别是具有大约1200kg/m3的密度。
在一个优选的实施方案中,根据本发明的矿棉产品为隔离产品。
在一个优选的实施方案中,根据本发明的矿棉产品的烧失量(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。
在一个实施方案中,矿棉产品为矿棉隔离产品,诸如矿棉隔热或隔音产品。
在一个实施方案中,矿棉产品为园艺栽培介质。
生产矿棉产品的方法
本发明还提供了一种通过用粘结剂组合物粘结矿物纤维来生产矿棉产品的方法。
根据本发明的矿棉产品的特别优点在于不需要高温进行固化。这不仅节省了能源,降低了VOC并且不需要耐高温的机械,但是在用这些粘结剂生产矿棉产品的过程中允许了更高的灵活性。
在一个实施方案中,该方法包括以下步骤:
-制备原料熔体,
-借助纤维成形装置纤维化熔体,以形成矿物纤维,
-提供聚集网(collected web)形式的矿物纤维,
-在提供聚集网之前、期间和之后,混合粘结剂和矿物纤维,以形成矿物纤维和粘结剂的混合物,
-固化矿物纤维和粘结剂的混合物。
在一个实施方案中,紧邻纤维成形装置,诸如一个转杯纺丝装置或级联纺丝装置,无论哪种情况在纤维形成之后立即提供粘结剂。其后,施加粘结剂的纤维作为网被传送到传送带上。
网可在纤维形成之后以及实质固化发生之前,经受纵向或长度方向压缩。
纤维成形装置
存在各种类型的离心纺纱机,用于纤维化矿物熔体。
常规离心纺纱机是级联纺纱机,其包括一系列的顶部(或第一)转子和后续(或第二)转子以及任选的其他后续转子(诸如第三转子和第四转子)。每个转子围绕不同的基本上水平的轴线旋转,其中转子的旋转方向与该系列中的相邻转子或每个相邻转子的旋转方向相反。不同水平轴被布置成使得将倾倒在顶部转子上的熔体按顺序被抛到后续转子或每个后续转子的周边表面上,并且纤维从后续转子或每个后续转子抛出,并且任选地也从顶部转子抛出。
在一个实施方案中,级联纺纱机或其他纺纱机被布置成纤维化熔体,并且纤维被夹带在空气中作为纤维云。
许多纤维成形装置包括围绕基本上垂直的轴线旋转的盘或杯子。然后通常将这些纺纱机中的几个串联布置,即基本上沿第一方向,例如GB-A-926,749、US-A-3,824,086和WO-A-83/03092中所述。
通常存在与该一个或每个纤维化转子相关联的空气流,由此当纤维从转子的表面上形成时被夹带在空气中。
在一个实施方案中,通过已知的手段将粘结剂和/或添加剂加入到纤维云。用于每个纺纱机的粘结剂和/或添加剂的量可以是相同的或不同的。
在一个实施方案中,烃油可加入到纤维云。
如本文所用,术语“聚集网”旨在包括任何已被收集聚拢在某一表面上的矿物纤维,即它们不再被气体携带,例如纤维化的矿物纤维、粒状、成簇或回收网废料。聚集网可以是通过收集传送带上的纤维而形成的、并作为起始物料提供而未被交叉折叠(cross-lap)或以其它方式固结的初次网。
或者,聚集网可以是通过将初次网交叉折叠或以其它方式固结而形成的二次网。优选的是,聚集网为初次网。
在一个实施方案中,在下列步骤中,在提供聚集网之后,完成粘结剂与矿物纤维的混合:
-对矿物纤维的聚集网进行解缠结处理,
-使矿物纤维悬浮在主气流中,
-在进行解缠结处理之前、期间或之后,将粘结剂混合物与矿物纤维混合,从而形成矿物纤维与粘结剂的混合物。
包括解缠结处理步骤的生产矿棉产品的方法在以引用方式并入的EP10190521中描述。
在一个实施方案中,解缠结处理包括将矿物纤维的聚集网从具有较低的相对气流的管道供给至具有较高的相对气流的管道。在该实施方案中,据信发生了解缠结,这是因为进入具有较高的相对气流的管道中的纤维首先受到拉力作用而与网中后续的纤维分开。这种类型的解缠结能够特别有效地制备开松的纤维簇,而不会产生可导致产品中的材料分布不均匀的致密团块。
根据一个特别优选的实施方案,解缠结处理包括:将聚集网供应到至少一个辊,该辊绕其纵轴旋转并具有从其圆周表面突出的尖状物。在该实施方案中,该旋转辊通常还至少部分地有助于产生所述较高的相对气流。通常,该辊的旋转是所述较高的相对气流的唯一源头。
在优选的实施方案中,从上方将矿物纤维和任选的粘结剂供应给辊。还优选的是,解缠结的矿物纤维和任选的粘结剂从辊的圆周的较低部分沿横向被抛离辊。在最优选的实施方案中,在矿物纤维被抛出之前,其被辊携带约180度。
可以在解缠结处理之前、期间或之后将粘结剂与矿物纤维混合。在一些实施方案中,优选的是,解缠结处理之前将粘结剂与纤维混合。特别是,纤维可以是未固化的含有粘结剂的聚集网的形式。
还可行的是,在解缠结处理之前,将粘结剂与矿物纤维的聚集网预混合。可以在解缠结处理期间和之后进行进一步的混合。或者,可以将该粘结剂单独提供至主气流并在主气流中混合。
通过任何合适的方式从主气流收集矿物纤维与粘结剂的混合物。在一个实施方案中,将主气流引入旋风室(cyclone chamber)的顶部,该旋风室的下端是打开的,并且从该旋风室的下端收集混合物。
优选将矿物纤维与粘结剂的混合物从解缠结处理过程投入到成形室中。
进行解缠结处理之后,收集矿物纤维与粘结剂的混合物并进行压制和固化。优选的是,将该混合物收集到在其下方设置有抽吸机构的有孔的传送带上。
在根据本发明的优选方法中,压制并固化收集的粘结剂和矿物纤维的混合物。
在根据本发明的优选方法中,粘结剂与矿物纤维的混合物被收集之后,在压制和固化之前,除去该混合物的表层。
可以以分批方式实施该方法,但是,根据一个实施方案,该方法是在矿棉生产线上进行的,其中将初次矿棉网或二次矿棉网供应到纤维分离处理工序中,这提供了特别成本有效且用途广泛的方法,该方法用以提供在广泛的密度范围内具有良好的机械特性和隔热特性的复合材料。
同时,由于在环境温度下固化,未固化的粘结剂的斑点的可能性明显下降。
固化
网是由粘结剂组分的化学和/或物理反应固化而成。
在一个实施方案中,固化发生在固化装置中。
在一个实施方案中,固化在5至95℃,诸如10至60℃、诸如20至40℃的温度下进行。
固化过程可在将粘结剂施加到纤维之后立即开始。固化被定义为粘结剂组合物经受化学反应,通常直到粘结剂组合物达到固态的过程,其中所述化学反应通常会增大粘结剂组合物中化合物的分子量并由此增加粘结剂组合物的粘度。
在一个实施方案中,固化过程包括交联和/或水作为结晶水的加入(inclusion)。
在一个实施方案中,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。
在一个实施方案中,固化在常规固化炉中进行,以用于在5至95℃,诸如10至60℃、诸如20至40℃的温度下操作矿棉生产。
在一个实施方案中,固化过程包括干燥过程,特别是通过吹空气或气体越过/穿过矿棉产品或通过升高温度。
在一个优选的实施方案中,与矿物纤维接触的粘结剂的固化发生在热压机中。
与矿物纤维在热压机中接触的粘结剂的固化的特别优点在于,能够制备高密度产品。
在一个实施方案中,固化过程包括压力干燥。压力可通过将空气或气体吹到矿物纤维和粘结剂的混合物中来施加。吹塑方法可伴随加热或冷却,或其可处于环境温度下。
在一个实施方案中,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。
矿棉产品可以在粘结剂固化之前、期间或之后,采用任何常规配置,例如垫或板坯,并且可被切割和/或成形(例如成管段)。
粘结剂组合物的优点
根据本发明的矿棉产品具有惊人的优点,其可通过非常简单的粘结剂产生,该粘结剂需要少至仅三种组分,即至少一种蛋白质、至少一种含酚和/或醌的化合物和至少一种脂肪酸甘油酯。因此,根据本发明的矿棉产品由天然和无毒组分生产,因此可安全使用。同时,根据本发明的矿棉产品由基于可再生资源的粘结剂制成,并且具有关于强度(未老化和老化的)和低吸水率的优异性能。
另一个优点是可以在环境温度或环境温度附近进行固化。这不仅节省了能量消耗并降低了所需机械的复杂性,而且还减少了在常规粘结剂的热固化过程中可能发生的未固化粘结剂斑点的可能性。
另一个优点是,引火(punking)风险显著降低。
引火可与矿棉制品的制造期间的放热反应有关,这会通过绝缘材料的厚度增加温度,导致矿物纤维的熔化或失透,并最终形成火灾隐患。在最坏的情况下,引火会导致仓库中存储的或运输期间的堆叠托盘中的火灾。
再一个优点是,固化期间不存在排放,特别是VOC排放。
另一个重要优点是,由粘结剂产生的矿棉产品的自我修复能力。
用根据本发明的粘结剂生产的矿棉产品的另一个优点是,在施加粘结剂之后但是固化之前可根据需要将其成形。这开辟了定制产品,如管段的可能性。
实施例
在下列实施例中,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。
用于根据现有技术的粘结剂组合物的测试方法
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施例)。在加入粘结剂混合物之前称取包含石棉盘的锡箔容器的重量,和在加入粘结剂混合物之后立即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个此类粘结剂混合物,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)稀释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。丸是与石棉纤维具有相同熔融组分的颗粒,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毫米至0.50毫米。
如上文“粘结剂固体”所述,获得包含0.5%粘结剂固体硅烷(Momentive VS-142)的15%粘结剂固体粘结剂溶液。将该粘结剂溶液的样品(16.0g)与丸(80.0g)充分混合。然后将所得混合物填充到耐热有机硅形式的四个插槽中,以制作小条(每个形式4×5插槽;插槽顶部尺寸:长=5.6cm,宽=2.5cm;插槽底部尺寸:长=5.3cm,宽=2.2cm;插槽高度=1.1cm)。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。将五个条在80℃的水浴中老化3h。
干燥1至2天后,在3点弯曲测试中将老化的条以及五个未老化的条折断(测试速度:10.0mm/min;破裂率:50%;标称强度:30N/mm2;支撑距离:40mm;最大挠度20mm;标称弹性模量10000N/mm2),该测试采用弯轨机(Bent Tram machine),研究其机械强度。将条放置在机器中,条的“顶面”(即尺寸长度=5.6厘米,宽度=2.5厘米的面)向上。
条的烧失量(LOI)
在小型锡箔容器中,通过在580℃下进行处理,测量条的烧失量(LOI)。对于每次测量,首先将锡箔容器在580℃下热处理15分钟,以去除所有有机物。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℃下被热处理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:
吸水率测量
通过对三个条进行称重,然后将条浸入烧杯(565mL,底部顶部高度=7.5cm)中的水(约250mL)中3小时或24小时,测量粘结剂的吸水率。将这些条彼此相邻地放置在烧杯的底部上,并使“顶面”朝下(即尺寸为长=5.6cm,宽=2.5cm的面)。在指定的时间量后,将条一个接一个地提起并使其向下滴落一分钟。保持(轻轻地)使条的长度侧几乎垂直,以使液滴从条的角部滴落。然后称重这些条,并使用以下公式计算吸水率:
现有技术的参考粘结剂组合物
粘结剂的实施例,参考粘结剂A(用脲改性的苯酚-甲醛树脂,PUF甲阶酚醛树脂)
通过以下来制备苯酚-甲醛树脂:在46%氢氧化钾(25.5g)水溶液的存在下,在84℃的反应温度下,使37%的甲醛(606g)水溶液和苯酚(189g)反应,通过大约1℃/分钟的加热速率达到84℃的反应温度。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在运动;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浑浊时,当摇动粘结剂时,浑浊不消失。
酸耐受性(AT)通过将用于滴定的酸的量(mL)除以样品的量(mL)来计算。
AT=(使用的滴定体积(mL))/(样品体积(mL))
使用获得的脲改性苯酚-甲醛树脂,通过加入25%的氨(90mL)水溶液和硫酸铵(13.2g)水溶液,随后加入水(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)。
用于根据本发明的粘结剂组合物和参考粘结剂的测试方法
对于根据本发明的粘结剂和参考粘结剂,确定了以下性能。
试剂
明胶(Speisegelatine,A型,猪,120和180布卢姆)得自Gelita AG公司。Tannorouge栗树单宁得自布罗兰bvba公司(Brouwland bvba)。椰子油、大麻油、橄榄油、油菜籽油和向日葵油得自Urtekram International A/S。亚麻籽油得自Borup Kemi I/S。桐油和所有其他组分均得自Sigma-Aldrich。除非另有说明,否则假定这些组分完全纯净且无水。
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:
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至20个条。丸是与石棉纤维具有相同熔融组分的颗粒,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。
如下面实施例中所述获得含有约15%粘结剂组分固体的粘结剂溶液。将该粘结剂溶液的样品(16.0g)与丸(80.0g;当与相对快速固化的粘结剂结合使用时,预热至40℃)充分混合。然后将所得混合物填充到耐热有机硅形式的四个插槽中,以制作小条(每个形式4×5插槽;插槽顶部尺寸:长=5.6cm,宽=2.5cm;插槽底部尺寸:长=5.3cm,宽=2.2cm;插槽高度=1.1cm)。在每个条的制造过程中,根据需要压制放置在插槽中的混合物,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16至20个条。然后将所得的条在室温下固化1至2天。然后将条小心地从容器中取出,倒置并在室温下放置一天以完全固化。将五个条在80℃的水浴中老化3小时。
干燥1至2天后,在3点弯曲测试中将老化的条以及五个未老化的条折断(测试速度:10.0mm/min;破裂率:50%;标称强度:30N/mm2;支撑距离:40mm;最大挠度20mm;标称弹性模量10000N/mm2),该测试采用弯轨机(Bent Tram machine),研究其机械强度。将条放置在机器中,条的“顶面”(即尺寸长度=5.6厘米,宽度=2.5厘米的面)向上。
条的烧失量(LOI)
在小型锡箔容器中,通过在580℃下进行处理,测量条的烧失量(LOI)。对于每次测量,首先将锡箔容器在580℃下热处理15分钟,以去除所有有机物。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℃下被热处理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:
吸水率测量
通过对三个条进行称重,然后将条浸入烧杯(565mL,底部0=9.5cm;顶部0=10.5cm;高度=7.5cm)中的水(约250mL)中3小时或24小时,测量粘结剂的吸水率。将这些条彼此相邻地放置在烧杯的底部上,并使“顶面”朝下(即尺寸为长=5.6cm,宽=2.5cm的面)。在指定的时间量后,将条一个接一个地提起并使其向下滴落一分钟。保持(轻轻地)使条的长度侧几乎垂直,以使液滴从条的角部滴落。然后称重这些条,并使用以下公式计算吸水率:
根据本发明的粘结剂组合物和参考粘结剂
粘结剂实施例,条目B
向在室温下搅拌的1M NaOH(15.75g)中,加入栗树单宁(4.50g)。在室温下再继续搅拌5至10分钟,得到深红褐色溶液。
在50℃下将明胶(Speisegelatine,A型,猪,120布卢姆,12.0g)在水(68.0g)中的混合物搅拌约15至30分钟直至获得澄清溶液(pH 5.0)。然后加入1M NaOH(4.37g)(pH9.1),然后加入上述栗树单宁溶液的一部分(5.40g;从而有效的是1.20g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3
向在室温下搅拌的1M NaOH(15.75g)中,加入栗树单宁(4.50g)。在室温下再继续搅拌5至10分钟,得到深红褐色溶液。
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(pH 5.1)。加入1M NaOH(4.00g)(pH 9.3),然后加入上述栗树单宁溶液的一部分(4.50g;从而有效的是1.00g栗树单宁)。然后在剧烈搅拌下加入椰子油(0.65g)。在50℃下剧烈搅拌约1分钟后,再次降低了搅拌速度,并且将所得褐色混合物(pH 9.3)用于随后的实验。
粘结剂实施例,条目5
向在室温下搅拌的1M NaOH(15.75g)中,加入栗树单宁(4.50g)。在室温下再继续搅拌5至10分钟,得到深红褐色溶液。
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(pH 4.8)。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;从而有效的是1.00g栗树单宁)。然后在剧烈搅拌下加入亚麻籽油(0.65g)。在50℃下剧烈搅拌约1分钟后,再次降低了搅拌速度,并且将所得褐色混合物(pH 9.2)用于随后的实验。
粘结剂实施例,条目6
向在室温下搅拌的1M NaOH(15.75g)中,加入栗树单宁(4.50g)。在室温下再继续搅拌5至10分钟,得到深红褐色溶液。
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(pH 4.8)。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;从而有效的是1.00g栗树单宁)。然后在剧烈搅拌下加入橄榄油(0.65g)。在50℃下剧烈搅拌约1分钟后,再次降低了搅拌速度,并且将所得褐色混合物(pH 9.1)用于随后的实验。
粘结剂实施例,条目9
向在室温下搅拌的1M NaOH(15.75g)中,加入栗树单宁(4.50g)。在室温下再继续搅拌5至10分钟,得到深红褐色溶液。
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(pH 4.8)。加入1M NaOH(4.00g)(pH 9.3),然后加入上述栗树单宁溶液的一部分(4.50g;从而有效的是1.00g栗树单宁)。然后在剧烈搅拌下加入桐油(0.16g)。在50℃下剧烈搅拌约1分钟后,再次降低了搅拌速度,并且将所得褐色混合物(pH 9.4)用于随后的实验。
粘结剂实施例,条目11
向在室温下搅拌的1M NaOH(15.75g)中,加入栗树单宁(4.50g)。在室温下再继续搅拌5至10分钟,得到深红褐色溶液。
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(pH 5.0)。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;从而有效的是1.00g栗树单宁)。然后在剧烈搅拌下加入桐油(1.13g)。在50℃下剧烈搅拌约1分钟后,再次降低了搅拌速度,并且将所得褐色混合物(pH 9.1)用于随后的实验。
粘结剂实施例,条目C
向在室温下搅拌的1M NaOH(15.75g)中,加入栗树单宁(4.50g)。在室温下再继续搅拌5至10分钟,得到深红褐色溶液。
在50℃下将明胶(Speisegelatine,A型,猪,180布卢姆,12.0g)在水(68.0g)中的混合物搅拌约15至30分钟直至获得澄清溶液(pH 5.0)。然后加入1M NaOH(3.81g)(pH9.1),然后加入上述栗树单宁溶液的一部分(5.40g;从而有效的是1.20g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 9.3)用于后续实验。
粘结剂实施例,条目12
向在室温下搅拌的1M NaOH(15.75g)中,加入栗树单宁(4.50g)。在室温下再继续搅拌5至10分钟,得到深红褐色溶液。
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(pH 5.0)。加入1M NaOH(3.28g)(pH 9.2),然后加入上述栗树单宁溶液的一部分(4.50g;从而有效的是1.00g栗树单宁)。然后在剧烈搅拌下加入桐油(0.65g)。在50℃下剧烈搅拌约1分钟后,再次降低了搅拌速度,并且将所得褐色混合物(pH 9.1)用于随后的实验。
表1-1:根据现有技术的粘结剂组合物
实施例 | 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 |
LOI,老化(%) | 2.8 |
吸水率,3h(%) | 4 |
吸水率,24h(%) | 8 |
表1-2:蛋白质、交联剂、矿物油或脂肪酸甘油酯
实施例 | B | 1 | 2 | 3 | 4 | 5 | 6 |
粘结剂组合物 | |||||||
蛋白质(重量%) | |||||||
明胶,Speisegelatine,120布卢姆 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
明胶,Speisegelatine,180布卢姆 | - | - | - | - | - | - | - |
交联剂(重量%)<sup>[a]</sup> | |||||||
栗树单宁 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
脂肪酸甘油酯(重量%)<sup>[a]</sup> | |||||||
矿物油 | - | 1.6 | 6.5 | - | - | - | - |
椰子油(碘值7至10) | - | - | - | 6.5 | - | - | - |
大麻油(碘值140至170) | - | - | - | - | 6.5 | - | - |
亚麻籽油(碘值136至178) | - | - | - | - | - | 6.5 | - |
橄榄油(碘值80至88) | - | - | - | - | - | - | 6.5 |
碱(重量%)<sup>[b]</sup> | |||||||
氢氧化钠 | 2.5 | 2.6 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
粘结剂混合和条制造 | |||||||
粘结剂组分固体含量(%) | 15.1 | 15.2 | 15.7 | 15.7 | 15.7 | 15.7 | 15.7 |
粘结剂混合物的pH | 9.1 | 9.1 | 9.1 | 9.3 | 9.1 | 9.2 | 9.1 |
固化温度(℃) | 室温 | 室温 | 室温 | 室温 | 室温 | 室温 | 室温 |
条特性 | |||||||
机械强度,未老化(kN) | 0.22 | 0.19 | 0.18 | 0.31 | 0.31 | 0.34 | 0.34 |
机械强度,老化(kN) | 0.17 | 0.12 | 0.12 | 0.25 | 0.24 | 0.30 | 0.28 |
LOI,未老化(%) | 2.9 | 2.9 | 2.9 | 3.0 | 3.0 | 3.0 | 3.0 |
LOI,水浴老化(%) | 2.6 | 2.6 | 2.7 | 2.8 | 2.8 | 2.8 | 2.8 |
吸水率,3h(%) | 16 | 18 | 16 | 10 | 10 | 9 | 10 |
吸水率,24h(%) | 31 | 31 | 32 | 23 | 24 | 23 | 22 |
[a]蛋白质的。[b]蛋白质+交联剂的。
表1-3:蛋白质、交联剂、脂肪酸甘油酯
实施例 | B | 7 | 8 | 9 | 10 | 11 | C | 12 |
粘结剂组合物 | ||||||||
蛋白质(重量%) | ||||||||
明胶,Speisegelatine,120布卢姆 | 100 | 100 | 100 | 100 | 100 | 100 | - | - |
明胶,Speisegelatine,180布卢姆 | - | - | - | - | - | - | 100 | 100 |
交联剂(重量%)<sup>[a]</sup> | ||||||||
栗树单宁 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
脂肪酸甘油酯(重量%)<sup>[a]</sup> | ||||||||
油菜籽油(碘值94至120) | - | 6.5 | - | - | - | - | - | - |
向日葵油(碘值118至144) | - | - | 6.5 | - | - | - | - | - |
桐油(碘值163至173) | - | - | - | 1.6 | 6.5 | 11.3 | - | 6.5 |
碱(重量%)<sup>[b]</sup> | ||||||||
氢氧化钠 | 2.5 | 2.5 | 2.5 | 2.6 | 2.5 | 2.4 | 2.3 | 2.2 |
粘结剂混合和条制造 | ||||||||
粘结剂组分固体含量(%) | 15.1 | 15.7 | 15.7 | 15.2 | 15.7 | 16.3 | 15.1 | 15.9 |
粘结剂混合物的pH | 9.1 | 9.1 | 9.2 | 9.4 | 9.1 | 9.1 | 9.3 | 9.1 |
固化温度(℃) | 室温 | 室温 | 室温 | 室温 | 室温 | 室温 | 室温 | 室温 |
条特性 | ||||||||
机械强度,未老化(kN) | 0.22 | 0.28 | 0.26 | 0.29 | 0.32 | 0.28 | 0.24 | 0.37 |
机械强度,老化(kN) | 0.17 | 0.25 | 0.21 | 0.22 | 0.22 | 0.21 | 0.17 | 0.34 |
LOI,未老化(%) | 2.9 | 2.9 | 3.0 | 2.9 | 3.0 | 3.1 | 2.9 | 3.0 |
LOI,水浴老化(%) | 2.6 | 2.8 | 2.8 | 2.7 | 2.9 | 3.0 | 2.8 | 2.9 |
吸水率,3h(%) | 16 | 11 | 10 | 11 | 8 | 8 | 13 | 9 |
吸水率,24h(%) | 31 | 25 | 24 | 24 | 23 | 20 | 25 | 22 |
[a]蛋白质的。[b]蛋白质+交联剂的。
Claims (27)
1.一种用于矿物纤维的无甲醛粘结剂组合物,包含:
-至少一种含酚和/或醌的化合物,
-至少一种蛋白质,
-至少一种脂肪酸甘油酯。
2.根据权利要求1所述的用于矿物纤维的粘结剂组合物,其中所述至少一种含酚和/或醌的化合物包含含酚化合物,诸如简单的酚类,诸如羟基苯甲酸,诸如羟基苯甲醛,诸如羟基苯乙酮,诸如羟基苯乙酸,诸如肉桂酸,诸如肉桂酸酯,诸如肉桂醛,诸如肉桂醇,诸如香豆素,诸如异香豆素,诸如色酮,诸如类黄酮,诸如查耳酮,诸如二氢查耳酮,诸如橙酮,诸如黄烷酮,诸如二氢黄酮醇,诸如黄烷,诸如无色花色素,诸如黄烷-3-醇,诸如黄酮,诸如花青素,诸如脱氧花青素,诸如花色素苷,诸如双黄酮,诸如二苯甲酮,诸如氧杂蒽酮,诸如芪类,诸如苯醌,诸如萘醌,诸如蒽醌,诸如甜菜红素,诸如多酚和/或多羟基酚,诸如木脂素、新木脂素(由偶联单木质醇诸如对香豆醇、松柏醇和芥子醇得到的二聚物或低聚物),诸如木质素(主要由单木质醇前体对香豆醇、松柏醇和芥子醇合成),诸如单宁,诸如缩合单宁(原花青素),诸如可水解单宁,诸如没食子单宁,诸如鞣花单宁,诸如复合单宁,诸如单宁酸,诸如鞣红,和/或含醌化合物,诸如苯醌,诸如萘醌,诸如蒽醌,诸如指甲花醌。
3.根据权利要求2所述的用于矿物纤维的粘结剂组合物,其中所述单宁选自单宁酸、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,和/或源自橡树、栗树、鹿角漆树和大穗杯花中的一种或多种的单宁。
4.根据上述权利要求中任一项所述的用于矿物纤维的粘结剂组合物,其中所述含酚和/或醌的化合物包含含有酚、多酚、醌的一种或多种合成或半合成分子,诸如用含酚和/或醌的侧链改性的蛋白质、肽、类肽、芳基类肽、聚苯乙烯,诸如用含酚和/或醌的侧链修饰的树形分子。
5.根据上述权利要求中任一项所述的用于矿物纤维的粘结剂组合物,其中所述至少一种蛋白质选自:来自动物来源的蛋白质,包括胶原、明胶、水解明胶和来自牛奶、鸡蛋中的蛋白质(酪蛋白、乳清);来自植物来源的蛋白质,包括来自豆类、谷物、全谷类、坚果、种子和水果中的蛋白质,如来自荞麦、燕麦、黑麦、小米、玉蜀黍(玉米)、大米、小麦、碾碎干小麦、高粱、苋属植物、藜麦、大豆的蛋白质(大豆蛋白)、扁豆、芸豆、白豆、绿豆、鹰嘴豆、豇豆、利马豆、木豆、羽扇豆、翼豆、杏仁、巴西坚果、腰果、碧根果、核桃、棉籽、南瓜籽、大麻籽、芝麻籽和向日葵籽;多酚蛋白质,诸如贻贝足丝蛋白质。
6.根据权利要求5所述的用于矿物纤维的粘结剂组合物,其中所述胶原或明胶源自哺乳动物、鸟类,诸如来自牛、猪、马、家禽和/或来自鱼鳞、鱼皮中的一种或多种来源。
7.根据权利要求2至6中任一项所述的用于矿物纤维的粘结剂组合物,其中所述单宁的含量基于蛋白质干重计为1重量%至70重量%,诸如2重量%至60重量%、诸如3重量%至50重量%、诸如4重量%至40重量%、诸如5重量%至35重量%。
8.根据上述权利要求中任一项所述的粘结剂组合物,其中所述蛋白质中的(赖氨酸+半胱氨酸)与所述含苯酚和/或醌的化合物中的(酚+醌)的质量比为1:5.78至1:0.08,诸如1:2.89至1:0.09、诸如1:1.93至1:0.12、诸如1:1.45至1:0.15、诸如1:1.16至1:0.17。
9.根据上述权利要求中任一项所述的粘结剂组合物,其中所述至少一种脂肪酸甘油酯为植物油和/或动物油的形式。
10.根据上述权利要求中任一项所述的粘结剂组合物,其中所述至少一种脂肪酸甘油酯为基于植物的油。
11.根据上述权利要求中任一项所述的粘结剂组合物,其中所述至少一种脂肪酸甘油酯选自亚麻籽油、橄榄油、桐油、椰子油、大麻油、油菜籽油和向日葵油构成的组中的一种或多种组分。
12.根据权利要求1至9中任一项所述的粘结剂组合物,其中所述至少一种脂肪酸甘油酯为动物油诸如鱼油的形式。
13.根据上述权利要求中任一项所述的粘结剂组合物,其中所述至少一种脂肪酸甘油酯包括碘值为≥75,诸如75至180、诸如≥130、诸如130至180的植物油和/或动物油。
14.根据权利要求1至11中任一项所述的粘结剂组合物,其中所述至少一种脂肪酸甘油酯包括碘值为≤100,诸如≤25的植物油和/或动物油。
15.根据上述权利要求中任一项所述的粘结剂组合物,其中所述脂肪酸甘油酯的含量基于蛋白质干重计为0.5重量%至40重量%,诸如1重量%至12重量%,诸如1.5重量%至15重量%,诸如3重量%至10重量%,诸如4重量%至7.5重量%。
16.根据上述权利要求中任一项所述的用于矿物纤维的粘结剂组合物,其中所述粘结剂组合物还包含选自由以下组成的组中的添加剂:氧化剂,诸如酪氨酸酶;金属离子,诸如铁离子;pH调节剂,优选地为碱的形式,诸如有机碱,诸如胺或其盐,无机碱,诸如金属氢氧化物,诸如KOH或NaOH、氨或其盐。
17.根据上述权利要求中任一项所述的用于矿物纤维的粘结剂组合物,其中所述粘结剂组合物的pH大于7,诸如大于8、诸如大于9。
18.根据上述权利要求中任一项所述的用于矿物纤维的粘结剂组合物,其中所述粘结剂组合物包含选自含有胺基团和/或硫醇基团的接头的至少一种添加剂。
19.一种矿棉产品,所述矿棉产品包含由粘结剂粘结的矿物纤维,所述粘结剂由根据权利要求1至18中任一项所述的粘结剂组合物的固化得到。
20.根据权利要求19所述的矿棉产品,其中所述矿棉产品的密度在10kg/m3至1200kg/m3,诸如30kg/m3至800kg/m3、诸如40kg/m3至600kg/m3、诸如50kg/m3至250kg/m3、诸如60kg/m3至200kg/m3的范围内。
21.根据权利要求19或20中任一项所述的矿棉产品,其中烧失量(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。
22.一种生产矿棉产品的方法,所述方法包括使矿物纤维与根据权利要求1至18中任一项所述的粘结剂组合物接触并且固化所述粘结剂的步骤。
23.根据权利要求22所述的生产矿棉产品的方法,其中所述方法包括以下步骤:
-制备原料熔体,
-借助纤维成形装置纤维化所述熔体,以形成矿物纤维,
-提供聚集网形式的所述矿物纤维,
-在提供所述聚集网之前、期间和之后,混合所述粘结剂组合物与所述矿物纤维,以形成矿物纤维和粘结剂组合物的混合物,
-固化所述矿物纤维和粘结剂组合物的混合物。
24.根据权利要求23所述的生产矿棉产品的方法,其中混合所述粘结剂与所述矿物纤维是在提供所述聚集网之后在以下步骤中进行的:
-对矿物纤维的所述聚集网进行解缠结处理,
-使所述矿物纤维悬浮在主气流中,
-在所述解缠结处理之前、期间或之后,将所述粘结剂与所述矿物纤维混合,从而形成矿物纤维与粘结剂的混合物。
25.根据权利要求22至24中任一项所述的生产矿棉产品的方法,其中所述固化在5℃至95℃,诸如10℃至60℃、诸如20℃至40℃的温度下进行。
26.根据权利要求22至25中任一项所述的生产矿棉产品的方法,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/穿过所述矿棉产品或通过升高温度。
27.根据权利要求1至18中任一项所述的粘结剂组合物用于生产矿棉产品的用途。
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CN111302392A (zh) * | 2020-04-02 | 2020-06-19 | 郑州大学 | 一种用于制备沸腾氯化炉用小球团料的有机粘结剂及方法 |
CN111302391B (zh) * | 2020-04-02 | 2022-07-29 | 郑州大学 | 一种全高钛渣制备沸腾氯化炉用小球团料的方法 |
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