CN103347917A - 基于聚异氰酸酯的粘合剂 - Google Patents

基于聚异氰酸酯的粘合剂 Download PDF

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Publication number
CN103347917A
CN103347917A CN2011800564437A CN201180056443A CN103347917A CN 103347917 A CN103347917 A CN 103347917A CN 2011800564437 A CN2011800564437 A CN 2011800564437A CN 201180056443 A CN201180056443 A CN 201180056443A CN 103347917 A CN103347917 A CN 103347917A
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binder composition
isocyanic ester
acid
polyisocyanate
water
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CN103347917B (zh
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D.利默肯斯
M.布勒克特
S.普里门
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Huntsman International LLC
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Huntsman International LLC
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Abstract

包含有机可乳化聚异氰酸酯、芳族聚酯多元醇和作为三聚催化剂的羧酸的碱金属盐的水性粘合剂组合物及其粘结矿物纤维或木质纤维材料的用途。

Description

基于聚异氰酸酯的粘合剂
本发明涉及适合用作木质纤维材料或矿物纤维,即人造玻璃质纤维(MMVF),例如玻璃熔渣(glass slag)或石棉(stone wool),即矿棉的粘合剂的组合物,用于提供此类组合物的方法,用此类粘合剂提供的产品和所述组合物作为矿物纤维或木质纤维材料的粘合剂的用途。
矿棉产品通常包含通过固化的热固性聚合材料粘结在一起的矿物纤维。将一股或更多股熔融玻璃、熔渣或石棉的流引入纤维并吹入成型室中,在成型室中它们以网的形式沉积到移动的传送带上。当纤维在成型室中空运时并且当纤维仍然热时,将纤维喷溅有粘合剂。然后将涂覆的纤维网从所述室运送至固化烘箱(150至320℃),在固化烘箱中通过垫吹入热空气以固化粘合剂并将矿棉纤维严格地粘结在一起。
在矿棉业中广泛使用苯酚-甲醛粘合剂,因为它们在未固化状态下具有低粘度,然而当固化时仍形成用于矿物纤维的刚性热固性聚合物基质。但是由于在工艺期间使用且释放不利于环境的化学品,苯酚-甲醛粘合剂的使用日益变得不期望。在粘合剂的应用和固化期间,将其提供至矿物纤维后,释放苯酚、甲醛和氨。一般而言,在纺成纤维的冷却中水的蒸发期间以及在烘箱中垫的干燥/固化期间损失所应用的苯酚-甲醛粘合剂的20至30 %;这些在然后需要被清理的浓缩的废水流中结束。
由US 4904522还已知的是使用聚异氰酸酯的水性分散体作为玻璃纤维的粘合剂。与已知苯酚/甲醛树脂相比,聚异氰酸酯粘合剂在低得多的温度下固化,不会分裂出挥发性单体,提供至少相同强度并且不是潜在的甲醛来源。
但是,US 4904522中公开的聚异氰酸酯粘合剂具有相对较高的量的未改性单体二异氰酸酯。因为单体二异氰酸酯的存在可导致工业卫生问题,尽可能降低单体二异氰酸酯的含量是有益的。
US 4904522中公开的聚异氰酸酯粘合剂的另一缺陷是在烘箱区中玻璃纤维垫的随后加热期间难以达到完全固化。在玻璃纤维垫的生产期间,将纤维用水性聚异氰酸酯粘合剂处理并连续贯穿烘箱区以便蒸发水和固化聚异氰酸酯树脂。当水性分散的聚异氰酸酯用作粘合剂时,水充当异氰酸酯基团的共反应物以形成聚脲。如果聚异氰酸酯粘合剂的异氰酸酯含量太高,则在反应完成之前水在烘箱区中蒸发,并作为结果获得未固化的、不能使用的玻璃纤维垫。
进一步的缺点是,尽管US 4904522的优选的聚异氰酸酯(即,聚苯基聚亚甲基聚异氰酸酯)在环境温度下呈低蒸气压,它们仍含有大量(多达70wt%)的单体二苯基甲烷二异氰酸酯。一旦暴露于烘箱区中的高温,这些单体二异氰酸酯可挥发,其导致排气中的高浓度。这表示如果这些排气逸入工作场所的大气或生产机构周围的空气中,则有环境危害。
避免未固化的聚异氰酸酯粘合剂的一种方法是将促进异氰酸酯/水反应的催化剂并入水性分散的聚异氰酸酯粘合剂中。但是,该方法也不会引起在烘箱区中水的蒸发之前聚异氰酸酯的完全固化和/或提供不可接受的低强度产品。
因此,本发明的目的是提供克服之前所述的粘合剂的缺陷的粘合剂。
根据本发明,提供包含有机聚异氰酸酯、异氰酸酯-反应性化合物以及促进异氰酸酯-三聚的催化剂的粘合剂组合物。所述组合物可用于粘结矿物纤维或木质纤维材料。
通过使用本发明的粘合剂组合物,在升高的温度下固化时进入环境的异氰酸酯释放大大降低并且几乎没有未反应的异氰酸酯留在最终产品中。异氰酸酯-反应性化合物与异氰酸酯反应并增加树脂的分子量从而预防蒸发。此外,调节三聚催化剂水平以获得改进的反应。
此外,甲醛排出降低相当大。
纤维玻璃垫可更快地固化,由此导致生产能力增加,而无大量投资。在较低固化温度下获得更快的生产,由此导致能源保护。
与现有技术产品相比,用本发明的粘合剂粘结的矿棉产品的结构强度增加,这提供降低树脂量同时获得相同性质的选择。
US 5372875描述了通过以下制备形成水性双组分聚氨酯组合物的方法:a)将具有至少12wt%的异氰酸酯含量的聚异氰酸酯分散于水中和b)在分散聚异氰酸酯之前、期间或之后,同样将聚羟基化合物与水混合,所述聚羟基化合物i)具有62至10000的分子量,ii)含有至少两个羟基基团,iii)为水溶性或水可分散性,iv)不含脲或氨基甲酸乙酯基团并且v)选自聚酯、聚内酯、聚碳酸酯、聚醚、聚硫醚、聚缩醛、聚醚酯、聚酯酰胺和聚酰胺的组,其中异氰酸酯基团与羟基基团的当量比为0.8:1至6:1。通过该方法制备的形成聚氨酯的组合物可用作玻璃纤维的粘合剂。
US 5372875提到添加促进异氰酸酯-羟基反应的催化剂但是未提及关于添加促进异氰酸酯的三聚的催化剂。
用于制备根据本发明的分散于水中的聚异氰酸酯的适合的聚异氰酸酯包括已知的脂肪族、环脂肪族、芳脂族、芳族和杂环聚异氰酸酯。
用作粘合剂的聚异氰酸酯的性质不是关键的,尽管它们应当具有高沸点以使得它们在100℃下不会以任何显著程度蒸发。与常规苯酚-甲醛树脂的情况一样,这防止了在胶粘剂硬化的应用期间显著的量的粘合剂挥发以及存在于排气中。
优选地,在分散于水中之前,聚异氰酸酯具有基于聚异氰酸酯的重量的至少12 %,优选至少约15 %和更优选至少约20 %或甚至至少约30wt%的异氰酸酯含量。具有较低的异氰酸酯含量并且例如通过使单体聚异氰酸酯与高分子量多元醇反应制备的聚异氰酸酯具有足够高的粘度使得难以将它们分散于水中,即使它们已经被亲水改性。
适合的单体聚异氰酸酯的实例包括1,6-六亚甲基二异氰酸酯、1,12-十二烷二异氰酸酯、环丁烷-1,3-二异氰酸酯、环己烷-1,3-和/或-1,4-二异氰酸酯、1-异氰酸基-3,3,5-三甲基-5-异氰酸基甲基环己烷(异佛尔酮二异氰酸酯)、2,4-和/或2,6-六氢甲代亚苯基二异氰酸酯、六氢-1,3-和/或-1,4-亚苯基二异氰酸酯、全氢-2,4'-和/或-4,4'-二苯基甲烷二异氰酸酯、1,3-和/或1,4-亚苯基二异氰酸酯、2,4-和/或2,6-甲代亚苯基二异氰酸酯,二苯基甲烷-2,4'-和/或-4,4'-二异氰酸酯、萘-1,5-二异氰酸酯、三苯基甲烷-4,4',4"-三异氰酸酯以及通过光气化苯胺/甲醛缩合产物而获得的聚苯基聚亚甲基聚异氰酸酯。
含有脲、缩二脲、氨基甲酸乙酯、脲基甲酸酯、脲二酮或碳二亚胺基团或异氰尿酸环的聚异氰酸酯加合物也是适合的。可通过已知方法,由任何已知单体聚异氰酸酯(尤其是上面列举的那些)来制备这些加合物。当使用低分子量、高挥发性二异氰酸酯时,尤其优选将这些二异氰酸酯转化为单体二异氰酸酯含量较低的加合物,之后将它们分散于水中。
还可能使用这些单体聚异氰酸酯和/或聚异氰酸酯加合物中任何的混合物。
一般而言,特别优选使用容易获得的聚异氰酸酯,如聚苯基聚亚甲基聚异氰酸酯(“粗MDI”或“聚合MDI”)以及含有碳二亚胺基团、氨基甲酸乙酯基团、脲基甲酸酯(allophonate)基团、异氰尿酸酯基团、脲二酮基团或缩二脲基团的聚异氰酸酯加合物,尤其是基于2,4-和/或2,6-甲代亚苯基二异氰酸酯(“TDI”)、1,6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯及其混合物的那些。
用于制备本发明的粘合剂组合物的聚异氰酸酯或聚异氰酸酯加合物可以它们的未改性、疏水形式使用,或者优选通过与外部乳化剂掺合或通过与含有异氰酸酯-反应性基团的阳离子、阴离子和/或非离子化合物反应而赋予其亲水性。确保聚异氰酸酯的分散性的反应组分包括含有侧面或末端、亲水环氧乙烷单元的化合物以及含有离子基团或潜在离子基团的化合物。
含有侧面或末端、亲水环氧乙烷单元的化合物含有至少一个,优选一个异氰酸酯-反应性基团并且以一定量使用,所述量足以提供基于聚异氰酸酯的重量至多约40wt%,优选约5至40wt%更优选约10至35wt%的亲水环氧乙烷单元的含量。含有离子基团或潜在离子基团的化合物含有至少一个,优选两个异氰酸酯-反应性基团,并且以每100 g聚异氰酸酯至多约120meq.,优选约5至80meq.,更优选约10至60meq.和最优选约15至50meq.的量使用。
除了化学并入聚异氰酸酯中的上述亲水改性剂以外,还可能使用可以是阴离子、阳离子或非离子的外部乳化剂。此外,当分散稳定性不是特定要求时,可能在不存在乳化剂下通过使用高剪切混合器将聚异氰酸酯分散于水中。
本发明中使用的聚异氰酸酯优选具有至少2,更优选至少2.2的官能度。可通过使具有大于2的官能度的聚异氰酸酯与含有亲水基团的单官能化合物反应来制备这些化合物,条件是平均官能度保持至少为2。
用于本发明的优选的聚异氰酸酯是所谓的可乳化聚异氰酸酯,尤其是可乳化MDI,如以下专利公开中所述:EP 18061、EP 516361、GB 1523601、GB 1444933、GB 2018796,其通过引用并入本文。
此类可乳化聚异氰酸酯可以商品名SUPRASEC 1041、SUPRASEC 1042、SUPRASEC 2405、SUPRASEC 2408、SUPRASEC 2419和RUBIN ATE 1780 (SUPRASEC和RUBIN ATE是来自Huntsman LLC的商标)由Huntsman商购获得。
在熔融/纤维化之后立即将粘合剂应用于纤维生产线时,水性粘合剂分散体或乳液中存在的水还用于冷却纤维。
对于高密度板材(密度通常高于100 kg/m3或者甚至高于200 kg/m3)的生产,有时使用冷纤维,并且在那些情况下可使用少量水或不使用水。
聚异氰酸酯分散体通常具有约2至100wt%,优选约2至96wt%,更优选约5至90wt%的固体含量。
对于冷纤维方法,固体含量通常为50至100wt%,对于热纤维方法,其通常为8至50wt%。
根据本发明,粘合剂组合物还含有一种或多种多官能异氰酸酯-反应性化合物,所述化合物优选为水溶性或者任选地在外部乳化剂存在下水可分散性。在随后的加热步骤中,多官能异氰酸酯-反应性化合物与聚异氰酸酯反应,在此期间水蒸发。
适合的多官能异氰酸酯-反应性化合物的实例包括聚羟基化合物、聚胺、硫醇、羧酸、脲和酰胺。
适合的聚羟基化合物通常具有62至10000的分子量;含有两个或多个羟基基团;为水溶性或者任选地在外部乳化剂存在下可分散于水中;并且选自聚羟基聚酯、聚内酯、聚碳酸酯、聚醚,聚硫醚、聚缩醛、聚醚酯、聚酯酰胺和聚酰胺。
已知聚羟基化合物来自聚氨酯化学并且通常具有400至10000,优选1000至6000的分子量。具有32至低于400的分子量的已知低分子量多元醇也是适合的。
相对于通过使用外部乳化剂赋予水溶性或水可分散性的那些,通过化学并入乳化剂赋予水溶性或水可分散性的聚羟基化合物的优点是:避免了将乳化剂与聚羟基化合物混合的额外的混合步骤。通过并入聚环氧乙烷单元、盐(离子)基团或潜在盐(离子)基团(随后在它们的制备期间被中和)可赋予任何前述聚羟基化合物水溶性或可分散性。
本发明中使用的优选的水溶性或水可分散性/可乳化聚羟基化合物是聚酯多元醇,尤其是芳族聚酯多元醇。使用芳族聚酯多元醇的益处是:用本粘合剂粘结的产品的燃烧性能也被改进。同样,芳族聚酯多元醇在最终产品的弯曲强度方面优于聚醚多元醇。
本发明中使用的其他适合的聚羟基化合物包括具有相对高环氧乙烷含量,优选至少为50或甚至至少为65wt%(基于聚醚多元醇的重量)的聚醚多元醇,如可商购获得的产品Perstorp P3380(来自Pertsorp Polyol)、DALTOCEL F526、F555、F442和F444(全部来自Huntsman),还包括由山梨糖醇起始的聚醚多元醇,例如可商购获得的Voranol G2005(来自Dow)。
在本发明中使用的聚酯多元醇有利地具有约1.8至8,优选约1.8至5并且更优选约2至2.5的平均官能度。它们的羟基数值通常落在约15至750、优选约30至550和更优选约200至550 mg KOH/g的范围内。优选地,聚酯多元醇具有0.1与20 mg KOH/g之间的酸数目;一般而言,酸数目可高达90 mg KOH/g。
可通过已知程序由多元羧酸或酸衍生物(例如多元羧酸的酸酐或酯)以及任何多元醇组分来制备聚酯多元醇。在聚酯多元醇的制备中多元酸和/或多元醇组分可作为两种或多种化合物的混合物使用。
多元醇可以为脂肪族、环脂肪族、芳族和/或杂环的。诸如具有不超过约20个碳原子的脂肪族二羟基醇的低分子量脂肪族多元醇是十分令人满意的。多元醇可任选地包括在反应中为惰性的取代基(例如,氯和溴取代基)和/或可以是不饱和的。也可使用适合的氨基醇,例如,单乙醇胺、二乙醇胺、三乙醇胺等。优选的多元醇是二醇。二醇可含有杂原子(例如硫二甘醇)或可仅由碳、氢和氧组成。它们有利地是通式为CnH2n(OH)2的简单二醇或如通式CnH2nO(OH)2表示的聚二醇,区别在于烃链中插入醚键。适合的聚羟基醇的实例包括:乙二醇、丙二醇-(1,2)和-(1,3)、丁二醇-(1,4)和-(2,3)、己二醇-(1,6)、辛二醇-(1,8)、新戊二醇、1,4-双羟甲基环己烷、2-甲基-1,3-丙烷二醇、甘油、三羟甲基乙烷、己三醇-(1,2,6)、丁三醇-(1,2,4)、醌醇、甲基葡萄糖苷、三甘醇、四甘醇以及更高级的聚乙二醇、二丙二醇以及更高级的聚丙二醇、二乙二醇、甘油、季戊四醇、三羟甲基丙烷、山梨糖醇、甘露醇、二丁二醇以及更高级的聚丁二醇。尤其适合的多元醇为亚烷基二醇和氧基亚烷基二醇,例如乙二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇、四甘醇、四丙二醇、三甲二醇、四甲二醇以及1,4-环己烷二甲醇(1,4-双-羟甲基环己烷)。
多元羧酸组分可以是脂肪族、环脂肪族、芳族和/或杂环的并且可以任选地被(例如)卤素原子取代和/或可以是不饱和的。用于制备聚酯多元醇的适合的羧酸及其衍生物的实例包括:草酸、丙二酸、己二酸、戊二酸、琥珀酸、庚二酸、辛二酸、壬二酸、癸二酸、苯二甲酸、苯二甲酸酐、对苯二酸酐、异苯二甲酸、对苯二甲酸、偏苯三酸、四氢苯二甲酸酐、苯均四酸二酐、六氢苯二甲酸酐、四氯苯二甲酸酐、内亚甲基四氢苯二甲酸酐、戊二酸酐、马来酸、马来酸酐、对苯二甲酸二甲酯、对苯二甲酸-双乙二醇酯、富马酸、任选地与诸如油酸的一元不饱和脂肪酸混合的二元和三元不饱和脂肪酸。
虽然聚酯多元醇可由基本上纯的反应物材料制备,然而可使用更复杂的成分,例如来自苯二甲酸、对苯二甲酸、对苯二甲酸二甲酯、聚对苯二甲酸乙二醇酯等的生产的侧流(side-stream)、废料或废弃残留物。这些组合物可通过与多元醇反应经常规酯交换或酯化程序转化为聚酯多元醇。
聚酯多元醇的生产通过简单地使多元羧酸或酸衍生物与多元醇组分以已知方式反应,直至反应混合物的羟基和酸数目落在所期望的范围内来实现。在酯交换或酯化后,反应产品可任选地与环氧烷反应。
如本文所使用,术语“聚酯多元醇”包括制备聚酯多元醇后剩余的任何少量的未反应的多元醇和/或在制备后添加的未酯化的多元醇(例如二醇)。聚酯多元醇可有利地包括至多约40wt%游离二醇。优选游离二醇含量为总聚酯多元醇组分的2至30,更优选2至15wt%。
在脂肪族聚酯多元醇中,用于制备聚酯多元醇的多元醇和多元羧酸均为脂肪族化合物。但是一些多元醇或多元羧酸可以是芳族性质的;脂肪族聚酯多元醇的芳香度(表示为每个分子含有至少一个芳环的基团的wt%)低于50 %。
在芳族聚酯多元醇中多元醇或多元羧酸的至少一种(优选酸)是芳族化合物并且芳香度为至少50 %。其酸组分有利地包含至少30wt%的苯二甲酸(或其异构体)残留物的聚酯多元醇是特别有用的。优选芳族聚酯多元醇的芳香度在70与90 %之间。
本发明中使用的优选的芳族聚酯多元醇包括STEPANPOL PS2352、PS3152和PS 1752,均可商购自Stepan;Hoopol F-1394、F-3362、F-4361、F-4396和F-7021,均可商购自Syntesia;以及Isoexter 3061、3557和4404,均可商购自Coim。
将聚羟基化合物以一定量添加至粘合剂组合物,所述量足以提供异氰酸酯基团与羟基基团(不考虑水的羟基基团)的2:1至30:1,优选5:1至10:1的当量比。
根据本发明,包括促进异氰酸酯三聚反应的催化剂是有利的。优选地,可将催化剂添加至聚羟基组合物或分散水中。
当固化阶段中所有水均已蒸发并且仍存在未反应的单体时,此类催化剂的添加是尤其有利的。然后剩余的单体可反应以形成聚异氰尿酸,导致粘合剂的完全固化。该反应还将迅速降低未反应的单体聚异氰酸酯的存在,所述单体聚异氰酸酯一旦暴露于固化烘箱中的高温就会挥发。
并入促进异氰酸酯/水反应(如US 5372875中所述)以避免剩余单体的催化剂在烘箱区中水蒸发之前不会引起聚异氰酸酯粘合剂的完全固化。此外,在垫形成阶段之前,添加较大量的异氰酸酯/水反应催化剂将导致粘合剂的初步固化。同样,结合产品的强度不令人满意。
催化异氰酸酯三聚反应(异氰尿酸-形成)的任何化合物可用作本发明中的三聚催化剂,例如叔胺,三嗪和最优选金属盐三聚催化剂。
特别优选的基团是有机羧酸的碱金属盐,例如乙酸钾(作为Polycat 46(来自Air Products)和催化剂LB(来自Huntsman)商购获得)或2-乙基己酸钾(作为Dabco K15(来自Air Products)商购获得),因为这些不会像含有催化剂的胺那样多地促进异氰酸酯/水反应。过度的异氰酸酯/水反应将导致初步固化。
通常以基于除水以外的总粘合剂配方0.001至10wt%,优选0.1至5wt%,最优选0.5至2.0wt%的量使用三聚催化剂。
除了促进三聚的催化剂以外,可添加控制聚氨酯固化的催化剂。但是在优选的实施方案中不存在此类催化剂。
此类适合的催化剂的实例为本身已知的那些并且包括叔胺(如三乙胺、三丙胺、三丁胺和三戊胺、N-甲基吗啉、N,N-二甲基环己胺、N,N-二甲基苄基胺、2-甲基咪唑、嘧啶、二甲基苯胺)和三乙二胺。含有异氰酸酯-反应性氢原子的叔胺的实例为三乙醇胺和N,N-二甲基乙醇胺。其他适合的催化剂为具有碳-硅键的硅杂胺(silaamine)和含氮碱如四烷基氢氧化铵;碱性氢氧化物、碱性酚盐和碱性醇盐。有机金属化合物(尤其是有机锡化合物)也可用作催化剂。
根据本发明,还可能使用反应抑制剂,例如诸如盐酸、有机酸或有机酸卤化物的酸。优选的酸为除了酸基团的一个以外含有另一异氰酸酯反应性氢原子的二羧酸或羧酸,以便得到至少2的官能度,以便起扩链剂或交联剂的作用。此类酸的实例为乳酸。乳酸将催化剂的活化温度转变为更高温度,从而避免将其在烘箱中加热(低密度垫)或热压制(高密度板材)之前树脂在纤维上的预固化。
通常基于除任何水以外的粘合剂组合物以0.1至2wt%范围内的量使用这些反应阻滞剂。
为改进纤维的润湿,可添加表面活性剂以降低乳液的表面张力。适合的张力活性剂为:树脂皂、饱和或不饱和脂肪酸、羟基硬脂酸钠、月桂基硫酸盐、烷基苯磺酸、直链烷基苯磺酸、烷基磺酸盐、聚氧乙烯烷基(苯基)醚、聚氧乙烯烷基(苯基)醚硫酸酯或其盐、聚氧乙烯烷基(苯基)醚磷酸酯或其盐、蛋白材料、烯基磺基琥珀酸和α-烯烃磺酸盐。其他适合的表面活性剂包括例如通过将10 mol或更多的环氧烷如环氧乙烷和环氧丙烷添加至分子中有6至30个碳原子的脂肪族一羟基醇(如十八醇和硬脂醇),或者添加至分子中有6至30个碳原子的脂环族一羟基醇,或者添加至分子中有6至30个碳原子的单价硫醇(如十二烷硫醇),或者添加至分子中有6至30个碳原子的烷基苯酚(例如壬基苯酚),或者添加至分子中有6至30个碳原子的胺(例如十二烷基胺),或者添加至分子中有6至30个碳原子的羧酸(例如月桂酸和硬脂酸)所形成的聚环氧烷衍生物;如通过具有磺酸基团的两个苯基基团的醚-连接所形成的烷基二苯醚磺酸盐,其可具有烷基或烷氧基基团作为取代基;各种类型的阴离子表面活性剂;各种类型的阳离子表面活性剂,如烷基胺乙酸盐和氯化烷基三甲基铵;各种类型的非离子表面活性剂;以及各种类型的两性表面活性剂。
优选作为表面活性剂的是聚醚改性的二甲基硅氧烷,最优选具有短硅氧烷链的那些。
也可将这些表面活性剂添加至异氰酸酯以降低其表面张力,并增加大部分水蒸发后的润湿能力。
基于除水以外的总粘合剂组合物以在0.01与1wt%之间变化的量使用此类表面活性剂。
标准结合添加剂可改进粘合剂。此类添加剂的实例包括:诸如硅烷的助粘剂(以改进在玻璃上的粘附)、稳定剂(以防止热或UV降解)以及表面活性化合物。
优选的助粘剂是氨基丙基硅烷。该物质可在水流中被添加并且将在乳化或分散阶段中非常快地与聚异氰酸酯反应。
也可应用诸如粘土、硅酸盐、硫酸镁的填充剂和诸如氧化钛的颜料,以及诸如硅烷、氟化合物、油、矿物质和硅油(反应性或非反应性)的疏水剂。
聚异氰尿酸酯本身已经比聚脲或聚氨酯更耐火,这是本发明的另外的优点,但不会限制附加阻燃剂的使用。
根据优选的实施方案,首先将聚羟基化合物、三聚催化剂和任选地其他添加剂添加至水。然后,优选刚好在应用于纤维之前通过在线混合将任选地还含有一些表面活性剂的聚异氰酸酯组合物与水性组合物混合。
优选的粘合剂组合物含有以下量范围的以下成分:
·可乳化MDI:100 pbw
·表面活性剂1(添加至聚异氰酸酯组合物):按粘合剂固体计0.1至1,优选0.5wt%
·水:0至2000 pbw
·三聚催化剂:按粘合剂固体计0.5至2.0,优选1.5wt%
·助粘剂:按粘合剂固体计0.2至2,优选0.5wt%
·表面活性剂2(添加至水性聚羟基组合物):按水计0.05至0.5,优选0.2wt%
·乳酸:按粘合剂固体计0.1至2.0,优选1.2wt%
·聚酯多元醇:20至60 pbw
本粘合剂组合物可与其他粘合剂组合物如苯酚-甲醛树脂、淀粉、改性淀粉、多糖、糠醛(fufural)、丙烯酸树脂、聚乙烯醇、纤维素和羧基甲基纤维素组合应用。
本粘合剂组合物可用于粘结各种材料,但优选用于粘结木质纤维材料或特别是矿物纤维。
如果用于粘结矿物纤维,优选将粘合剂组合物喷溅在熔融玻璃纤维或岩石纤维上,和随后通常在150与260℃之间,优选约150至170℃的温度下固化。与现有技术粘合剂相比本粘合剂组合物的一个优点是:可使用较低固化温度,这也会降低树脂损失的可能性。
可将粘合剂溶液喷溅到纤维上,其中可能使用外围的和中间的喷雾器。由于异氰酸酯与水(异氰酸酯在其中乳化)反应,优选的加工方法是在喷嘴处或刚好在喷嘴之前混合两种组分,以防止胶凝或沉淀反应。
粘合剂通常基于矿棉纤维以2至10 %,优选4至8 %,甚至更优选4至5wt%(除水以外)范围的量应用于纤维。
矿棉板(像抑尘剂、着色剂、添味剂、填充剂等)的生产中通常使用的其他添加剂可被单独添加或通过混合于一股或更多股稀释的粘合剂流中来添加。
但是,还可能在绝缘材料生产的随后步骤中,例如通过将其喷溅到传送带上的原网上,或者甚至在较晚阶段将粘合剂应用于矿棉。在这种单独且较晚阶段还可能应用其它粘合剂,从而获得具有改进的耐性和/或强度的材料。还可能在干混合方法中将粘合剂分布于干的冷纤维上。然后可使粘合剂在相对低的温度下固化。
可以以常规方式,例如在气体加热炉中或在电炉中或在竖炉或化铁炉中将纤维组合物的原材料转化为熔体。可以以常规方式,例如通过转杯方法或通过串联转子方法将熔体转化为纤维。
人造玻璃质纤维(MMVF)由例如石头、熔渣、玻璃或其他熔体制造。通过在炉内熔融具有期望的分析的矿物组合物来形成熔体。这种组合物通常通过混合岩石或矿物以给出期望的分析来形成。
纤维可具有任何适当的纤维直径和长度。通常,平均纤维直径低于10 μm,例如5 μm。通常,矿棉产品含有1至20wt%干粘合剂,优选1至15wt%,最优选2至10wt%。通常,在熔体刚刚纤维化之后,将粘合剂添加至纤维。通常,矿棉产品呈厚片、薄片或其他成型制品形式。
使用本发明的粘合剂制造的矿棉板的密度通常在5至2500 kg/m3,优选120至1200 ± 150 kg/m3范围内。
根据本发明的产品可配制用于MMV纤维的任何常规目的,例如,厚片、薄片、管或其他形状的产品,所述产品将充当隔热、隔火和防火或降低和控制噪音或充当园艺生长介质。
粘合剂还可用于涂覆纤维的表面或者矿棉产品的一个或多个表面。
本发明的粘合剂组合物也可用作玻璃纤维产品的胶粘剂。
本粘合剂组合物的另一应用是在木质纤维材料的粘结中。
通过使木质纤维部分与粘合剂组合物接触来制备木质纤维主体,其通过以下方式:将组合物混合、喷溅和/或平铺于木质纤维部分之中/之上,以及通过挤压木质纤维部分,优选通过热挤压,通常在80℃至300℃,优选140℃至270℃以及0.1至6 MPa特定压力下。
这些结合方法通常是本领域已知的。
在华夫板生产中,可通过将本粘合剂组合物喷溅于木质纤维材料上同时将其搅拌来方便地混合木质纤维材料与粘合剂组合物。
在中密度纤维板中,可通过在如通常所用的喷放管道(blowline)中将本粘合剂组合物喷溅于木质纤维材料上来方便地混合木质纤维材料和粘合剂组合物。
在一种生产方法中,用粘合剂组合物处理木质纤维材料后将其置于由铝或钢制造的d垫板(caul plate)上,所述垫板用来将经树脂处理的配料运入挤压机,在挤压机中通常在120℃与300℃之间,优选140℃与270℃之间的温度下将其压缩至期望的程度(指定厚度或密度)。在开始生产运行时,通过用外部脱模剂喷溅于压板的表面或增加第一挤压机加载的循环时间来调节压盘可能是有用的,但并非必需。然后,在本发明的方法中可多次使用预先调节的压制机而无需进一步处理。
可在华夫板(也称为定向刨花板)、中密度纤维板、颗粒板(也称为木屑板)、木纤维绝缘板材以及胶合板的生产中使用该方法。
因此所用的木质纤维材料可包括木质束(wood strand)、木屑、木纤维、刨花、薄木片、木丝、软木、树皮、锯屑等木材加工行业的废料产品以及具有诸如纸、甘蔗渣、稻草、亚麻、剑麻、竹、椰子纤维、大麻、灯心草、芦苇、稻壳、果壳、草、坚果壳等的木质纤维主要成分的其他材料。此外,与木质纤维材料混合的其他微粒或纤维材料为如磨碎的泡沫废料(例如,磨碎的聚氨酯泡沫废料)、矿物填料、玻璃纤维、云母、橡胶、诸如塑料纤维和织物的纺织废料。这些材料可以颗粒、刨花或片、纤维、线、球或粉末形式使用。
将粘合剂组合物应用于木质纤维材料时,粘合剂/木质纤维材料的重量比将取决于所采用的木质纤维材料的堆密度而变化。因此,可以此量应用粘合剂组合物以得到0.1:99.9至25:75范围内,和优选在0.5:99.5至10:90范围内并且最优选在2:98至8:92或者甚至1.5:98.5至6:94范围内的粘合剂/木质纤维材料的重量比。
本发明的各方面由以下实施例说明,但不受其限制。
在这些实施例中使用以下成分:
SUPRASEC 1042:可乳化MDI,由Huntsman获得
催化剂LB:羧酸三聚催化剂的碱金属盐,由Huntsman获得
Dabco K15:羧酸三聚催化剂的碱金属盐,由Air Products获得
Dabco TMR:季铵盐三聚催化剂,由Air Products获得
Jeffcat TR90:胺催化剂,由Huntsman获得
Stepanpol PS2352:芳族聚酯多元醇,羟基数目240,由Stepan获得
DALTOCEL F526:聚醚多元醇,羟基数目128,由Huntsman获得
DALTOCEL F442:聚醚多元醇,羟基数目42,由Huntsman获得
DALTOCEL F444:聚醚多元醇,羟基数目35,由Huntsman获得
CAPA 2043:己内酯聚酯二醇,羟基数目280,由Perstorp获得
ISOEXTER 3644:溴化的芳族聚酯多元醇,羟基数目300,由Coim获得
ISOEXTER 3061:芳族聚酯多元醇,羟基数目300,由Coim获得
Eternacoll BH100:聚碳酸酯二醇,羟基数目116,由UBE Chemical Europe获得。
实施例
制备含有如下表所列出的成分的粘合剂制剂(量表示为pbw)。首先将所有添加剂添加至水中,和然后使用内嵌静态混合装置将该水性分散体与聚异氰酸酯混合。
在表中所示温度下发生固化。通过TGA测定树脂损失百分数。
根据标准DIN 63测量粘合剂量为3%的板的弯曲强度。
结果示于下表中。

Claims (19)

1.粘合剂组合物,其包含有机聚异氰酸酯、异氰酸酯-反应性化合物和促进异氰酸酯-三聚的催化剂。
2.根据权利要求1所述的粘合剂组合物,其中固体含量为2至100wt.%。
3.根据权利要求1或2所述的粘合剂组合物,其还含有水。
4.根据权利要求3所述的粘合剂组合物,其为水性乳液或分散体形式。
5.根据上述权利要求的任一项所述的粘合剂组合物,其中将所述聚异氰酸酯改性以使其可乳化或可分散。
6.根据权利要求5所述的粘合剂组合物,其中所述改性涉及与含有异氰酸酯-反应性基团的阳离子、阴离子和/或非离子化合物的反应。
7.根据上述权利要求的任一项所述的粘合剂组合物,其中所述聚异氰酸酯来源于二苯基甲烷二异氰酸酯(MDI)和/或其低聚物。
8.根据上述权利要求的任一项所述的粘合剂组合物,其中所述异氰酸酯-反应性化合物包含芳族聚酯多元醇。
9.根据上述权利要求的任一项所述的粘合剂组合物,其中所述异氰酸酯-反应性化合物的量足以提供异氰酸酯基团与羟基基团(除水以外)的2:1至30:1,优选5:1至20:1的当量比。
10.根据上述权利要求的任一项所述的粘合剂组合物,其中所述促进异氰酸酯-三聚的催化剂是羧酸的碱金属盐。
11.根据上述权利要求的任一项所述的粘合剂组合物,其中以基于所述粘合剂固体的0.1至5wt.%范围内的量使用所述促进异氰酸酯-三聚的催化剂。
12.根据上述权利要求的任一项所述的粘合剂组合物,其还包含反应抑制剂和/或润湿剂和/或助粘剂。
13.根据权利要求12所述的粘合剂组合物,其中所述反应抑制剂是乳酸。
14.用于制备根据权利要求2至13所述的粘合剂组合物的方法,其包括以下步骤:将所述异氰酸酯-反应性化合物、所述促进异氰酸酯-三聚的催化剂以及任选的其他添加剂添加至水中,并将所述水性组合物与任选地含有一些表面活性剂的所述聚异氰酸酯混合。
15.用于提供结合的矿物纤维产品的方法,其包括以下步骤:施用如权利要求1至13的任一项中所定义的粘合剂组合物至矿物纤维,并使所述粘合剂固化。
16.根据权利要求15所述的方法,其中所述固化在150至260℃,优选150至170℃的温度发生。
17.根据权利要求15或16所述的方法,其中以基于所述矿物纤维的2至10%,优选4至8wt.%(除水以外)范围的量应用所述粘合剂组合物。
18.一种矿物纤维产品,其可通过权利要求15至17中任一项所述的方法获得。
19.用于提供结合的木质纤维产品的方法,其包括以下步骤:使所述木质纤维部分与如权利要求1至13的任一项中所定义的粘合剂组合物接触,和通过挤压所述木质纤维部分,优选通过热挤压。
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