CN105176460A - 碳水化合物多胺粘合剂及用其制备的材料 - Google Patents
碳水化合物多胺粘合剂及用其制备的材料 Download PDFInfo
- Publication number
- CN105176460A CN105176460A CN201510524023.7A CN201510524023A CN105176460A CN 105176460 A CN105176460 A CN 105176460A CN 201510524023 A CN201510524023 A CN 201510524023A CN 105176460 A CN105176460 A CN 105176460A
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- China
- Prior art keywords
- polyamines
- composite wood
- wood board
- tackiness agent
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000000034 method Methods 0.000 claims abstract description 43
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- 238000006243 chemical reaction Methods 0.000 claims description 58
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- 125000000217 alkyl group Chemical group 0.000 claims description 36
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Abstract
披露了一种包含碳水化合物反应物与多胺的产物的粘合剂。该粘合剂适用于固结松散组装的物质,例如纤维。披露了包含与碳水化合物反应物及多胺接触的纤维的未固化纤维产品。粘合剂组合物可固化以产生包含由交联聚合物粘合的纤维的纤维产品。进一步披露了用于以基于碳水化合物反应物及多胺的粘合剂粘合纤维的方法。
Description
本申请是申请号为201180022853.X,申请日为2011年5月7日,发明名称为“碳水化合物多胺粘合剂及用其制备的材料”的分案申请。
相关申请的交叉引用
本申请要求2010年5月7日提交的美国临时申请61/332,458的权益,该申请以引用的方式并入本文中。
技术领域
本发明涉及一种粘合剂制剂及以其制得的包含基于碳水化合物的粘合剂的材料及其制备方法。具体而言,描述了包含碳水化合物反应物与多胺的反应产物的粘合剂及以其制得的材料。
背景技术
粘合剂因为其能够固结非组装或松散组装的物质而适用于制造物品。举例而言,粘合剂能使两个或两个以上表面粘结起来。具体而言,粘合剂可用于制造包含固结纤维的产物。热固性粘合剂的特征可在于通过加热或催化作用转化成不溶且难熔的材料。热固性粘合剂的实例包括多种苯酚-醛、脲-醛、三聚氰胺-醛及其他缩合-聚合材料,如呋喃及聚氨酯树脂。含有苯酚-醛、间苯二酚-醛、苯酚/醛/脲、苯酚/三聚氰胺/醛等的粘合剂组合物用于粘结纤维、织物、塑料、橡胶及许多其他材料。
历史上,矿棉及纤维板工业曾使用苯酚甲醛粘合剂来粘合纤维。苯酚甲醛型粘合剂使最终产品具有适合的性质;然而,环境考虑推动了替代性粘合剂的发展。一种此类替代性粘合剂为由碳水化合物与多质子酸反应获得的基于碳水化合物的粘合剂,例如美国公开申请第2007/0027283号及公开的PCT申请WO2009/019235。另一替代性粘合剂为多羧酸与多元醇反应的酯化产物,例如美国公开申请第2005/0202224号。因为此类粘合剂不利用甲醛作为试剂,所以其统称为无甲醛粘合剂。
当前发展的一个领域为寻找用于建筑及汽车部门的全部范围产品(例如玻璃纤维隔离、粒子板、办公台及隔音)中苯酚甲醛型粘合剂的替代物。具体而言,先前所开发的无甲醛粘合剂可能不具有用于此部门中所有产品的所有所需性质。举例而言,基于丙烯酸及聚(乙烯醇)的粘合剂已显示出有前景的性能特征。然而,此类粘合剂与苯酚甲醛粘合剂相比相对较昂贵,基本上由基于石油的资源获得,且与基于苯酚甲醛的粘合剂组合物相比具有展现较低反应速率的倾向(需要延长固化时间或升高固化温度)。基于碳水化合物的粘合剂组合物由相对廉价的前体制成,且主要由再生性资源获得;然而,此类粘合剂亦可能需要基本上不同于传统苯酚甲醛粘合剂系统固化的条件的固化反应条件。因此,利用现有替代物顺畅地替代苯酚甲醛型粘合剂并不容易实现。
发明内容
根据本发明,描述了基于碳水化合物的粘合剂。粘合剂组合物具有使其适用于多种应用的性质;具体而言,粘合剂可用于粘合松散组装的物质,例如纤维。
在说明性实施方式中,本发明涉及包含碳水化合物反应物与多胺的聚合物产物的粘合剂。在一个实施方式中,碳水化合物反应物为多醣。在一个实施方式中,碳水化合物反应物为单醣或二醣。在另一实施方式中,碳水化合物为这样的单醣,该单糖为其醛醣或酮醣形式。在另一实施方式中,碳水化合物反应物选自右旋糖、木糖、果糖、二羟基丙酮及其混合物。在另一实施方式中,聚合物产物为热固性聚合物产物。
在说明性实施方式中,多胺为伯多胺。在一个实施方式中,多胺可为具有式H2N-Q-NH2的分子,其中Q为烷基、环烷基、杂烷基或环杂烷基,其各自可任选被取代。在一个实施方式中,Q为选自C2至C24的烷基。在另一实施方式中,Q为选自C2至C8的烷基。在另一实施方式中,Q为选自C3至C7的烷基。在另一实施方式中,Q为C6烷基。在一个实施方式中,Q选自环己基、环戊基或环丁基。在另一实施方式中,Q为苄基。
在说明性实施方式中,多胺选自二胺、三胺、四胺及五胺。在一个实施方式中,多胺为选自1,6-二氨基己烷及1,5-二氨基-2-甲基戊烷的二胺。在一个实施方式中,二胺为1,6-二氨基己烷。在一个实施方式中,多胺为选自二亚乙基三胺、1-哌嗪乙胺或双(六亚甲基)三胺的三胺。在另一实施方式中,多胺为四胺,例如三亚乙基四胺。在另一实施方式中,多胺为五胺,例如四亚乙基五胺。
在说明性实施方式中,伯多胺为聚醚-多胺。在一个实施方式中,聚醚-多胺为二胺或三胺。
在说明性实施方式中,碳水化合物反应物与多胺的重量比在约1:1至约30:1的范围。在另一实施方式中,碳水化合物反应物与多胺的重量比在约2:1至约10:1的范围。在另一实施方式中,聚合物产物的水性萃取物具有在约5至约9范围的pH值。在另一实施方式中,聚合物产物的水性萃取物基本上无色。在另一实施方式中,聚合物产物不含苯酚和/或不含甲醛。在另一实施方式中,聚合物产物的水性萃取物能够还原本尼迪克试剂(Benedict'sreagent)。在另一实施方式中,聚合物产物吸收400nm与500nm之间(例如420nm)的光。
在一说明性实施方式中,制造以聚合物粘合剂粘合的物质集合体的方法包括:制备含有用于制造聚合物粘合剂的反应物及溶剂的溶液,其中反应物包括碳水化合物反应物及多胺;将溶液置于物质集合体上;使溶剂挥发以形成未固化产品,及使未固化产品经受使碳水化合物反应物与多胺聚合形成聚合物粘合剂的条件。在一个实施方式中,物质集合体包含选自以下的纤维:矿物纤维(渣棉纤维、石棉纤维或玻璃纤维)、芳酰胺纤维、陶瓷纤维、金属纤维、碳纤维、聚酰亚胺纤维、聚酯纤维、人造丝纤维及纤维素纤维。在另一实施方式中,物质集合体包含颗粒,例如煤或砂石。在另一实施方式中,物质集合体为玻璃纤维。在另一实施方式中,玻璃纤维以约70重量%至约99重量%的范围存在。在另一实施方式中,物质集合体包含纤维素纤维。举例而言,纤维素纤维可为木刨花、锯屑、木浆或碎木。在另一实施方式中,纤维素纤维可为其他天然纤维,例如黄麻、亚麻、大麻及秸秆。
在说明性实施方式中,制造以聚合物粘合剂粘合的物质集合体的方法进一步包括:通过分别添加一定量的碳水化合物反应物与一定量的多胺以使重量比在约2:1至约10:1的范围来制备溶液。在一个实施方式中,制备溶液包括将碳水化合物反应物与多胺添加至水溶液中。在另一实施方式中,制备溶液包括将溶液的pH值调节至约8至约13的范围,例如约8至约12的范围。
在说明性实施方式中,本发明涉及包含物质集合体及粘合剂的组合物;粘合剂包含碳水化合物反应物与多胺之间反应的聚合物产物,聚合物产物基本上不溶于水。在一个实施方式中,物质集合体包括矿物纤维(渣棉纤维、石棉纤维或玻璃纤维)、芳酰胺纤维、陶瓷纤维、金属纤维、碳纤维、聚酰亚胺纤维、聚酯纤维、人造丝纤维及纤维素纤维。举例而言,纤维素纤维包括木刨花、锯屑、木浆和/或碎木。在一个实施方式中,碳水化合物反应物选自右旋糖、木糖、果糖、二羟基丙酮及其混合物。在另一实施方式中,多胺选自二胺、三胺、四胺及五胺。在一个实施方式中,多胺为H2N-Q-NH2,其中Q为烷基、环烷基、杂烷基或环杂烷基,其各自任选被取代。在另一实施方式中,组合物进一步包含含硅化合物。在一个实施方式中,含硅化合物为官能化甲硅烷基醚或官能化烷基甲硅烷基醚,例如氨基官能化烷基甲硅烷基醚。举例而言,在一个实施方式中,含硅化合物可为γ-氨基丙基三乙氧基硅烷、γ-缩水甘油氧基丙基三甲氧基硅烷或氨基乙基氨基丙基三甲氧基硅烷或其混合物。在另一实施方式中,含硅化合物可为氨基官能性低聚硅氧烷。在另一实施方式中,组合物包含选自以下的腐蚀抑制剂:除尘油、磷酸一铵、偏硅酸钠五水合物、三聚氰胺、乙二酸锡(II)及甲基氢聚硅氧烷流体乳液。
附图说明
图1展示梅拉德反应(Maillardreaction)的示意图,其结束于类黑精的产生。
图2展示代表性阿马多里重排(Amadorirearrangement)的示意图。
图3展示在使用具有204℃的温度控制压板的模压机进行的热模制循环期间(X轴为模制时间,以分钟为单位),对于不同粘合剂,玻璃纤维毡片样品中心的固化温度特征(Y轴,以℃为单位)。粘合剂1(◆)为苯酚甲醛粘合剂(比较例2);粘合剂2(■)为碳水化合物-无机酸粘合剂(比较例3);且粘合剂3(X)为右旋糖-氨-己二胺(HMDA)粘合剂(实施例5)。
详细说明
尽管本发明易受各种改进及替代形式影响,但本文中将详细描述特定实施方式。然而应了解,不欲将本发明限于所述特定形式,而是相反,意欲涵盖属于本发明的精神及范畴内的所有修改、等同物及替代物。
本发明涉及在固结非组装或松散组装物质方面具有出乎意料的效用的粘合剂组合物。在粘合剂组合物领域的当前技术状态下,该粘合剂组合物提供出乎意料的进步。具体而言,粘合剂提供性能的改进且提供更简化且有利的制造方法,同时维持基于碳水化合物的粘合剂系统所特有的完善的环境优势。
如本文中所使用的术语粘合剂溶液为基本上可脱水形成未固化粘合剂的化学物质的溶液。如本文中所用,粘合剂或粘合剂组合物可为固化、未固化或部分固化的。未固化粘合剂的组合物称为未固化粘合剂组合物。未固化粘合剂为可固化形成固化粘合剂的化学物质的基本上脱水的混合物。基本上脱水意谓使用于制备粘合剂溶液的溶剂(通常为水或其混合物)蒸发至使剩余材料(包含粘合剂反应物及溶剂)的粘度足够高以在松散组装物质之间建立粘着的程度;因此,剩余材料为未固化粘合剂。在一个实施方式中,溶剂少于剩余材料总重量的65%。在另一实施方式中,基本上脱水的粘合剂具有总粘合剂的约5重量%与约65重量%水之间的水分含量。在另一实施方式中,溶剂可少于剩余材料总重量的50%。在另一实施方式中,溶剂可少于剩余材料总重量的35%。在另一实施方式中,基本上脱水的粘合剂具有总粘合剂的约10重量%与约35重量%之间的水。在另一实施方式中,溶剂可占剩余材料总重量的约20%。
在说明性实施方式中,未固化粘合剂可为至少部分可溶于水的无色、白色、灰白色、赭石色或黄色至淡褐色的粘性物质。如本文中所使用的,术语固化粘合剂描述使未固化粘合剂组合物固化获得的聚合物产物。固化粘合剂可具有特征性的棕色至黑色颜色。尽管描述为棕色或黑色,但另一特征为粘合剂倾向于吸收广泛范围波长的光。具体而言,可在约420nm下存在较高吸光度。随着聚合物广泛交联,固化粘合剂基本上不溶。举例而言,粘合剂大部分不溶于水。如本文所述,未固化粘合剂提供足够的粘合能力来固结纤维;然而,固化粘合剂赋予通常与交联聚合物相关的稳固性、长期耐久性及物理性质。
在说明性实施方式中,本文所述的粘合剂反应物可溶于水且粘合剂溶液为粘合剂反应物于水溶液中的溶液。在一个实施方式中,在水溶液中包括表面活性剂以增加一或多种粘合剂反应物或添加剂的溶解度或分散性。举例而言,表面活性剂可添加至粘合剂水溶液中以增强颗粒添加剂的分散性。在一个实施方式中,使用表面活性剂来形成具有非极性添加剂或粘合剂反应物的乳液。在另一实施方式中,粘合剂溶液包含以粘合剂溶液的重量计约0.01重量%至约5重量%的表面活性剂。
在说明性实施方式中,本文所述的粘合剂溶液可在制造矿物纤维绝缘产品期间涂覆于矿物纤维上(例如随着毡片或纤维进入成形区域而喷洒于毡片上或喷洒于纤维上)。一旦粘合剂溶液与矿物纤维接触,则来自矿物纤维的残余热量(注意,玻璃纤维例如由熔融玻璃制造且因此含有残余热量)及穿过产品和/或产品周围的空气流将引起部分水自粘合剂溶液蒸发。移除水使得纤维上粘合剂的剩余组分成为粘性或半粘性高固含量混合物的涂层。此粘性或半粘性高固含量混合物的涂层充当粘合剂。此时,毡片尚未固化。换言之,未固化粘合剂起作用以粘合毡片中的矿物纤维。
此外,应了解上述未固化粘合剂可进行固化。举例而言,制造固化隔离产品的方法可包括施加热量来在未固化粘合剂组合物中引起化学反应的后续步骤。举例而言,在制备玻璃纤维绝缘产品或其他矿物纤维绝缘产品的情况下,在粘合剂溶液已涂覆于纤维且脱水之后,可将未固化绝缘产品转移至固化烘箱中。在固化烘箱中,加热未固化绝缘产品(例如约300℉至约600℉[约150℃至约320℃]),引起粘合剂固化。固化粘合剂为不含甲醛的防水粘合剂,其将绝缘产品的纤维粘合在一起。应注意,干燥及热固化可相继、同时、同期或并行进行。
在说明性实施方式中,未固化纤维产品包含约3%至约40%的干燥粘合剂固体(以总未固化固体重量计)。在一个实施方式中,未固化纤维产品包含约5%至约25%的干燥粘合剂固体。在另一实施方式中,未固化纤维产品包含约50重量%至约97重量%的纤维。
如本文中关于矿物纤维上的粘合剂所提及,固化粘合剂为固化粘合剂反应物的产物。术语固化表示粘合剂已暴露于起始化学变化的条件。此类化学变化的实例包括(但不限于)(i)共价键合、(ii)粘合剂组分的氢键合、及(iii)粘合剂中的聚合物和/或低聚物的化学交联。此类变化与未固化粘合剂相比可增强粘合剂的耐久性及耐溶剂性。使粘合剂固化可导致形成热固性材料。另外,固化粘合剂与未固化粘合剂相比可引起集合中物质之间的粘着增强。固化可通过例如热、微波辐射和/或引发一或多种上述化学变化的条件引发。尽管不限于特定理论,但固化可包括碳水化合物与多胺反应形成类黑精。
在粘合剂中的化学变化引起水释放的情形中(例如聚合及交联),固化可由仅因干燥出现的以上所释放的水的量来确定。用于测量与在粘合剂进行固化时相比干燥期间所释放的水的量的技术为本领域中所熟知。
本发明的一个方面为固化粘合剂组合物包含含氮聚合物。含氮聚合物在颜色上为棕色至黑色。虽然不限于特定理论,但固化粘合剂组合物包含类黑精。类黑精可鉴别为复杂的含呋喃环及含氮的棕色高分子量聚合物。如本文中所用的高分子量包括分子量超过100,000道尔顿的聚合物。在包含高度交联聚合链时,本文所述的类黑精的分子量接近无限大。因此,类黑精的分子量可为所分析聚合物的质量及物理尺寸的函数。举例而言,具有3克质量的类黑精的整体样品可假定由于广泛交联而包含单一聚合分子。因此,聚合物的分子量将为约每摩尔1.8×1024克(为样品质量与’阿佛加德罗常数的乘积)。如本文中所用,高分子量聚合物包括具有大致在每摩尔约1×105克与每摩尔约1×1024克之间的分子量的聚合物。
尽管不限于特定理论,但已知类黑精根据反应物及制备条件可具有结构变化。亦已知类黑精具有随着加热的温度及时间而增加的碳氮比率。此外,类黑精具有饱和、不饱和及芳族性质。对于类黑精,不饱和度及芳族性随着加热的温度(固化温度)及时间(固化时间)而增加。类黑精亦在类黑精内的多种结构中含有作为反应物并入的糖的C-1。类黑精亦可含有羰基、羧基、胺、酰胺、吡咯、吲哚、甲亚胺、酯、酐、醚、甲基和/或羟基。根据结构的复杂性,红外光谱法可适用于鉴别此类官能基中的一种或多种。尽管本文中描述为类黑精型聚合物,但本领域技术人员应了解,粘合剂亦可根据所存在特定键的存在进行分类,例如聚酯、聚醚、聚酰胺等。
可表征粘合剂的另一方式为分析固化粘合剂热解期间所产生的气态化合物。本发明范畴内的固化粘合剂的气体热解可产生约0.5%至约15%(根据相对峰面积)的一或多种以下化合物:2-环戊烯-1-酮、2,5-二甲基-呋喃、呋喃、3-甲基-2,5-呋喃二酮、苯酚、2,3-二甲基-2-环戊烯-1-酮、2-甲基苯酚、4-甲基苯酚、2,4-二甲基-苯酚、邻苯二甲酸二甲酯、十八酸或芥子酸酰胺。使用己二胺作为多胺组分所制备的粘合剂样品在770℃下进行的热解气相色谱分析(PyGC-MS)的指纹图谱显示吡啶及许多组分,所述组分为吡咯或吡啶衍生物(甲基吡啶、甲基吡咯、二甲基吡啶、二甲基吡咯、乙基甲基吡咯及其他吡咯相关含氮组分)。可鉴别粘合剂的另一方式为含有粘合剂的溶液(或萃取物溶液)是否能够还原本尼迪克试剂。在一个实施方式中,与粘合剂或其水性萃取物接触的溶液可还原本尼迪克试剂。
本发明的一个方面为本文所述的粘合剂在环境上友好。与不断修订的政府法规相对应,本发明描述可制成不含甲醛的粘合剂。另外,本文所述的化学物质基本上不含甲醛及苯酚。在此意义上,甲醛及苯酚均不用作本发明范畴内的试剂。尽管可添加该两者来获得具有潜在适用性质的粘合剂,但本发明的一个方面为可制成不含此两种反应物的粘合剂。在另一方面中,本发明的粘合剂组合物可在不使用挥发性反应物下进行制造。在一个实施方式中,伯胺及碳水化合物都为非挥发性反应物。如本文中所用,挥发性反应物为在20℃下蒸气压大于10kPa的。类似地,如本文中所用,非挥发性反应物在20℃下具有小于约10kPa的蒸气压。具体而言且作为一实例,本发明粘合剂可在不添加氨或释放氨的化合物下进行制造。在一个实施方式中,多胺在60℃下具有小于约0.5kPa的蒸气压。
本发明的另一环境友好的方面为粘合剂的初级反应物为碳水化合物。碳水化合物视为再生性资源。然而,现有技术主要使用石油来源的反应物用于制造粘合剂组合物。在另一方面中,粘合剂经由与现有技术中所描述的相当体系相比可在较低温度下进行化学反应制备。因此,固化烘箱及制造设备可在较低温度下操作,从而节省有价值的资源。在替代方案中且以相关方式,本文所述的粘合剂与目前使用的相当粘合剂相比当经受类似固化温度时固化更快速。因此,经由任一方法,本发明的一个方面为使用本发明所披露的粘合剂形成的产品与根据现有技术制备的相当粘合剂(例如基于苯酚甲醛的产品)相比碳足迹可基本上降低。
除环境效益外,本发明的粘合剂组合物及以其制得的材料可制成具有等效于或超过相当粘合剂体系(例如苯酚甲醛粘合剂)的性能特征的性能特征。在一个方面中,本发明的粘合剂使以其制得的物品具有足够拉伸强度,从而允许在OEM应用中进行刀模切割、制造、层压及安装。在一个方面中,本发明的粘合剂具有与苯酚甲醛粘合剂的防水性相当的防水性(耐候性)。可与特定应用相关的其他性能特征包括产品排放、密度、灼烧减量、厚度恢复、尘埃、拉伸强度、分离强度、分离强度的耐久性、粘结强度、吸水性、热表面性能、钢腐蚀性、抗挠刚度、韧性-刚性、抗压强度、条件抗压强度、压缩模量、条件压缩模量及灼烧烟气发展。本发明的一个方面为固化粘合剂的萃取物基本上为pH值中性,例如pH值在6与8之间。本发明的另一方面为本发明粘合剂能够制造具有与苯酚甲醛粘合剂组合物相当的相关性能特征的产品。
作为说明,在一个实施方式中,本发明粘合剂具有产生基本上无色水性萃取物的优势。本发明的此特征使粘合剂在例如天花板瓷砖、家具或办公台的应用中合乎需要,其中成品可与水接触。以本发明粘合剂制得的固化制造商品在接触湿气或水之后显示优良的耐变色性或防渗色性。此外,在该种实施方式中,接触粘合剂的水并不在其接触粘合剂之后可能接触的其他物品或部分上留下残留颜色。举例而言,在一个实施方式中,粘合剂可在办公台应用中用于粘合玻璃纤维。粘合玻璃纤维组合物可被淡色织物覆盖。有利的是,在一个实施方式中,接触玻璃纤维组合物的水并不在办公台干燥之后在织物上留下有色残余物。
除性能特征外,涉及本发明所披露的粘合剂的制造工艺及方法具有许多出乎意料的优于先前所描述的粘合剂的优势。在一个方面中,如先前关于环境效益所述,本发明粘合剂可在不使用高度挥发性反应物下进行制造。因此,制造排放控制处于较低负荷。此外,反应效率较高,因为由于蒸发造成的反应物损耗降低。因此,本发明的一个方面为本文中所用的化合物为基本上非挥发性化合物,因此使须采用以减轻不当排放的步骤减少。
根据另一方面,反应形成粘合剂的反应物反应足够缓慢以使得可使用一步式/一锅式粘合剂系统。根据此方面,反应物化合物反应足够缓慢以使得其可添加至单一反应物溶液中且储存合理时间量,在此期间,其可使用一个分布系统涂覆于产品上。这与在较低温度下反应从而在粘合剂溶液传递系统中产生不溶性反应产物的粘合剂系统形成对照。如此处所用,在不发生显著的(大于5%)聚合物沉淀下储存的合理时间量为两周。
本发明的另一方面为尽管粘合剂在室温条件下充分不起反应以有助于一锅式方法,但其在高温下充分反应以在极低温度和/或极短固化滞留时间下固化。一方面,较低固化温度降低绝缘产品经历无焰燃烧和/或造成线路着火的风险。如此处所用,极低温度的特征为低于或等于约120℃。如此处所用,极短固化时间为少于或等于约4分钟。
在说明性实施方式中,粘合剂组合物包括酸或酸盐以增加未固化粘合剂或粘合剂溶液的存放期。尽管此酸不为反应物或催化剂,但可包括其以在储存条件下维持粘合剂溶液或未固化粘合剂时减缓或抑制粘合剂反应物形成粘合剂。举例而言,挥发性酸或酸盐可包括在粘合剂溶液或未固化粘合剂中以减缓或抑制环境条件下的固化反应。然而,可通过加热粘合剂溶液或未固化粘合剂来去除酸使得酸挥发且增加粘合剂溶液或未固化粘合剂的pH值。在一个实施方式中,粘合剂组合物包括延长存放期用的酸。在另一实施方式中,粘合剂组合物中延长存放期用的酸与多胺的摩尔比为约1:20至约1:1。
本发明的另一方面为具有满足或超过在相当用途范畴内可比苯酚及甲醛类型粘合剂可显示的固化速率的固化速率、周期及固化温度的粘合剂。在此方面,本发明粘合剂可在不改造设备下用作应用中苯酚甲醛树脂的直接替代物。此外,本发明粘合剂能够改变固化温度及时间以使得反应温度及固化时间均可降低。此降低具有降低工艺的总体能量消耗及减少制造产品时的环境影响的作用。此外,较低固化温度具有增强制造工艺的安全性的另一作用。较低固化温度的另一作用为降低无焰燃烧或着火的风险。
在绝缘产品的制造中,由放热固化反应释放的热量可能引起产品的自我加热。只要热量自产品耗散,自我加热通常不成问题。然而,若热量使产品温度增加至氧化过程开始的点时,自我加热可能引起对产品的明显损害。举例而言,无焰燃烧或氧化可在绝缘产品的温度超过约425℉(210℃)时发生。在此类温度下,放热燃烧或氧化过程促进进一步自我加热且可能破坏粘合剂。此外,温度可增至可能使玻璃纤维熔合或反玻化的程度。此情形不仅损害绝缘产品的结构及价值,其亦可能造成火灾。
本发明的另一方面为在添加或不添加腐蚀抑制剂下,粘合剂体系基本上为非腐蚀性。此外,粘合剂体系并不需要添加任何有机或无机酸或其盐作为催化剂或活性成分。因此,本发明粘合剂的一个方面为其可制成基本上不含酸。此外,粘合剂可在完全碱性条件下制造。如此处所用,术语酸包括特征主要为其酸性特性的化合物,例如多质子无机及有机酸(例如硫酸及柠檬酸)。此方面降低制造设备的磨损及维护需求且增强工作者安全性。
在说明性实施方式中,粘合剂包含碳水化合物反应物与多胺的聚合物产物。如本文中所使用的,术语碳水化合物反应物系指单醣、二醣、多醣或其反应产物。在一个实施方式中,碳水化合物反应物可为还原糖。如本文中所用,还原糖指示一种或多种含有醛基或可异构化(亦即互变异构化)从而含有醛基的糖,所述基团可以例如Cu+2氧化以提供羧酸。亦应了解,任何此类碳水化合物反应物均可任选被例如羟基、卤基、烷基、烷氧基等基团取代。此外应了解,在任何此类碳水化合物反应物中,存在一个或多个手性中心,且各手性中心的两种可能的光学异构体预期均包括于本文所述的本发明中。此外,亦应了解各种混合物(包括外消旋混合物或任何此类碳水化合物反应物的各种光学异构体的其他非对映异构性混合物以及其各种几何异构体)均可用于本文所述的一个或多个实施方式中。虽然非还原糖(例如蔗糖)可能并非较佳,但其可通过原位转化成还原糖(亦即蔗糖到转化糖的转化为本领域中已知的方法)而仍适用于本发明的范畴内。此外,亦应了解单醣、二醣或多醣可部分与前体反应形成碳水化合物反应产物。在碳水化合物反应产物衍生自单醣、二醣或多醣且维持类似的与多胺的反应性形成与单醣、二醣或多醣与多胺的反应产物类似的反应产物的程度上,碳水化合物反应产物在术语碳水化合物反应物的范畴内。
在一个方面中,任何碳水化合物反应物应足够不挥发以使其保持可用于与多胺反应的能力达到最大。碳水化合物反应物可为呈醛醣或酮醣形式的单醣,包括丙醣、丁醣、戊醣、己醣或庚醣;或多醣;或其组合。举例而言,当丙醣用作碳水化合物反应物或与其他还原糖和/或多醣组合使用时,可使用醛丙醣或酮丙醣,分别例如甘油醛及二羟基丙酮。当丁醣用作碳水化合物反应物或与其他还原糖和/或多醣组合使用时,可使用醛丁醣,例如赤藻糖及苏糖;及酮丁醣,例如赤藻酮糖。当戊醣用作碳水化合物反应物或与其他还原糖和/或多醣组合使用时,可使用醛戊醣,例如核糖、阿拉伯糖、木糖及来苏糖;及酮戊醣,例如核酮糖、阿拉伯酮糖、木糖及来糖。当己醣用作碳水化合物反应物或与其他还原糖和/或多醣组合使用时,可使用醛己醣,例如葡萄糖(亦即右旋糖)、甘露糖、半乳糖、阿洛糖、阿卓糖、塔罗糖、古洛糖及艾杜糖;及酮己醣,例如果糖、阿洛酮糖、山梨糖及塔格糖。当庚醣用作碳水化合物反应物或与其他还原糖和/或多醣组合使用时,可使用酮庚醣,例如景天庚酮糖。已知为非天然存在的碳水化合物反应物的其他立体异构体亦预期适用于制备本文所述的粘合剂组合物。在一个实施方式中,碳水化合物反应物为高果糖玉米糖浆。
在说明性实施方式中,碳水化合物反应物为多醣。在一个实施方式中,碳水化合物反应物为具有低聚合度的多醣。在一个实施方式中,多醣为糖蜜、淀粉、纤维素水解产物或其混合物。在一个实施方式中,碳水化合物反应物为淀粉水解产物、麦芽糊精或其混合物。虽然较高聚合度的碳水化合物可能不为较佳,但其可通过原位解聚(亦即在高温下经由氨化解聚为本领域中已知的方法)而仍适用于本发明的范畴内。
此外,碳水化合物反应物可与非碳水化合物多羟基反应物组合使用。可与碳水化合物反应物组合使用的非碳水化合物多羟基反应物的实例包括(但不限于)三羟甲基丙烷、甘油、异戊四醇、聚乙烯醇、部分水解的聚乙酸乙烯酯、完全水解的聚乙酸乙烯酯及其混合物。在一个方面中,非碳水化合物多羟基反应物足够分不挥发以使其保持可用于与单体或聚合多胺反应的能力达到最大。应了解非碳水化合物多羟基反应物的疏水性可为确定如本文所述制备的粘合剂的物理性质的一个因素。
如本文中所用,多胺为具有两个或两个以上氨基的有机化合物。如本文中所用,伯多胺为具有两个或两个以上伯氨基(-NH2)的有机化合物。可原位改性或异构化产生具有两个或两个以上伯氨基(-NH2)的化合物的化合物在术语伯多胺范畴内。在说明性实施方式中,多胺为伯多胺。在一个实施方式中,伯多胺可为具有式H2N-Q-NH2的分子,其中Q为烷基、环烷基、杂烷基或环杂烷基,其各自可任选被取代。在一个实施方式中,Q为选自C2至C24的烷基。在另一实施方式中,Q为选自C2至C8的烷基。在另一实施方式中,Q为选自C3至C7的烷基。在另一实施方式中,Q为C6烷基。在一个实施方式中,Q选自环己基、环戊基或环丁基。在另一实施方式中,Q为苄基。
如本文中所使用的术语“烷基”包括任选支化的碳原子链。如本文中所使用的术语“烯基”及“炔基”包括任选支化且分别包括至少一个双键或三键的碳原子链。应了解炔基亦可包括一个或多个双键。另外应了解,烷基有利地具有有限长度,包括C1-C24、C1-C12、C1-C8、C1-C6及C1-C4。另外应了解,烯基和/或炔基有利地各自具有有限长度,包括C2-C24、C2-C12、C2-C8、C2-C6及C2-C4。本文中应了解,较短烷基、烯基和/或炔基可给化合物增加较少亲水性且因此对碳水化合物反应物将具有不同反应性及在粘合剂溶液中将具有不同溶解度。
如本文中所使用的术语“环烷基”包括任选支化的碳原子链,其中至少一部分链呈环状。应了解环烷基烷基为环烷基的子集。应了解环烷基可为多环。说明性环烷基包括(但不限于)环丙基、环戊基、环己基、2-甲基环丙基、环戊基乙-2-基、金刚烷基等基团。如本文中所使用的术语“环烯基”包括任选支化且包括至少一个双键的碳原子链,其中至少一部分链呈环状。应了解一个或多个双键可在环烯基的环状部分和/或环烯基的非环状部分中。应了解环烯基烷基及环烷基烯基各为环烯基的子集。应了解环烷基可为多环。说明性环烯基包括(但不限于)环戊烯基、环己基乙烯-2-基、环庚烯基丙烯基等基团。另外应了解成链环烷基和/或环烯基有利地具有有限长度,包括C3-C24、C3-C12、C3-C8、C3-C6及C5-C6。本文中应了解较短烷基和/或烯基成链环烷基和/或环烯基分别可给化合物增加较少亲脂性且因此将具有不同特性。
如本文中所使用的术语“杂烷基”包括包含碳及至少一个杂原子且任选支化的原子链。说明性杂原子包括氮、氧及硫。在某些变化形式中,说明性杂原子亦包括磷及硒。在一个实施方式中,杂烷基为聚醚。如本文中所使用的术语“环杂烷基”(包括杂环基及杂环)包括包含碳及至少一个杂原子(例如杂烷基)且任选支化的原子链,其中至少一部分链为环状。说明性杂原子包括氮、氧及硫。在某些变化形式中,说明性杂原子亦包括磷及硒。说明性环杂烷基包括(但不限于)四氢呋喃基、吡咯烷基、四氢吡喃基、哌啶基、吗啉基、哌嗪基、高哌嗪基、奎宁环基等基团。
如本文中所用的术语“任选被取代”包括在任选被取代的基团上氢原子经其他官能基替换。作为说明,所述其他官能基包括(但不限于)氨基、羟基、卤基、硫醇基、烷基、卤烷基、杂烷基、芳基、芳基烷基、芳基杂烷基、硝基、磺酸及其衍生物、羧酸及其衍生物等基团。作为说明,氨基、羟基、硫醇基、烷基、卤烷基、杂烷基、芳基、芳基烷基、芳基杂烷基和/或磺酸中的任一种任选被取代。
在说明性实施方式中,伯多胺为二胺、三胺、四胺或五胺。在一个实施方式中,多胺为选自二亚乙基三胺、1-哌嗪乙胺或双(六亚甲基)三胺的三胺。在另一实施方式中,多胺为四胺,例如三亚乙基四胺。在另一实施方式中,多胺为五胺,例如四亚乙基五胺。
伯多胺的一个方面为其可具有低空间位阻。举例而言,1,2-二氨基乙烷、1,4-二氨基丁烷、1,5-二氨基戊烷、1,6-二氨基己烷、1,12-二氨基十二烷、1,4-二氨基环己烷、1,4-二氨基苯、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、1-哌嗪乙胺、2-甲基-戊二胺、1,3-戊二胺及双(六亚甲基)三胺以及1,8-二氨基辛烷具有本发明范畴内的低空间位阻。一个实施方式为1,6-二氨基己烷(己二胺)。另一实施方式为1,5-二氨基-2-甲基戊烷(2-甲基-戊二胺)。在另一实施方式中,伯多胺为聚醚-多胺。在另一实施方式中,聚醚-多胺为二胺或三胺。在一个实施方式中,聚醚-多胺为平均分子量为440的三官能性伯胺,称为JeffamineT-403聚醚胺(HuntsmanCorporation)。
在一个实施方式中,多胺可包括聚合多胺。举例而言,本发明范畴内的聚合多胺包括壳聚糖、聚赖氨酸、聚亚乙基亚胺、聚(N-乙烯基-N-甲基胺)、聚氨基苯乙烯及聚乙烯胺。在一个实施方式中,多胺包含聚乙烯胺。如本文中所用,聚乙烯胺可为均聚物或共聚物。
虽然不限于特定理论,但本发明的一个方面为伯多胺及碳水化合物反应物为反应形成类黑精产物的梅拉德(Maillard)反应物。图1显示梅拉德反应的示意图,其结束于类黑精的产生。在其初始阶段中,梅拉德反应涉及碳水化合物反应物,例如还原糖(注意碳水化合物反应物可能来自能够在梅拉德反应条件下产生还原糖的物质)。反应亦涉及使碳水化合物反应物(例如还原糖)与胺反应物(亦即具有氨基的化合物)缩合。换言之,碳水化合物反应物及胺反应物为梅拉德反应的类黑精反应物。此两种组分的缩合产生N-取代的葡基胺。关于梅拉德反应的更详细描述请参见Hodge,J.E.ChemistryofBrowningReactionsinModelSystemsJ.Agric.FoodChem.1953,1,928-943,其披露内容以引用的方式并入本文中。关于梅拉德反应的文献着重于自氨基酸产生类黑精。本发明与此类参考文献的不同之处可在于并非所有氨基酸为多胺。视为本发明范畴内的多胺的常见氨基酸包括天冬酰胺、谷氨酰胺、组氨酸、赖氨酸及精氨酸。
不受理论束缚,将更详细描述多胺与碳水化合物反应物之间的共价反应。如本文所述,本发明反应的路径因以下原因而不同于现有技术的教导:(1)本发明反应可在碱性pH值下进行完全,(2)多胺在其针对碳水化合物反应物的反应性中为双官能,(3)多胺经由其双官能反应性或另一未知现象显示出反应范畴内的较低活化能量,其导致反应速率的意外提高和/或使反应进行时的温度降低。
自多胺与碳水化合物反应物形成类黑精中的第一步骤为碳水化合物反应物与多胺缩合。证据表明,本文所述的条件尤其适于驱使反应完成。首先,据信粘合剂溶液的碱性驱动缩合。举例而言,已显示糖与胺在水溶液中与所用胺的碱性强度或溶液的pH值成比例经历变棕。据信N-经取代的醣苷胺在水溶液中在明显程度上保持不解离。因此,必须考虑不解离分子所经历的不可逆转化。虽然已知缩合反应为可逆的,但发现此反应可根据勒沙特列原理通过将粘合剂溶液同时脱水来进一步驱动完成。照此,确定未固化粘合剂组合物的初始主要组分为伯多胺的N-糖基衍生物。
再次参照图1,粘合剂反应物转化为类黑精产物的第二步骤为所谓阿马多里重排。代表性阿马多里重排的示意图展示于图2中。参照图2,伯多胺的N-糖基衍生物与席夫碱的阳离子处于平衡。虽然平衡有利于N-醣苷胺,但已知席夫碱的阳离子进一步重排为烯醇或酮形式系自发地进行。发现此自发反应由脱水进一步促进,因为速率在脱水样品中提高。本发明的一个方面为伯多胺的结构尤其通过使化合物呈席夫碱的阳离子形式时所获得的正电荷稳定来加速此重排。据信此稳定作用在现有技术或文献中尚未论述,因为使用伯多胺的增强作用先前尚未披露。因此,本发明的一个方面为伯多胺在阿马多里重排期间提供席夫碱的阳离子稳定性的类型。在另一方面中,伯多胺当处于基本上干燥的状态下时在阿马多里重排期间提供席夫碱的阳离子稳定性的类型。
本发明的另一方面为亦据信碳水化合物结构影响阿马多里重排的动力学。具体而言,已知当结晶N-经取代醣苷胺的C-2羟基未经取代时,化合物在储存期间缓慢转化成阿马多里重排产物。然而,若C-2羟基经取代,则重排显著受到抑制。因此,本发明的一个方面为本发明的碳水化合物在C-2羟基处未取代。本发明的一个方面为未固化粘合剂组合物包含呈烯醇及酮形式的N-醣苷胺、1-氨基-1-脱氧-2-酮醣的混合物。再次参照图1,在形成呈烯醇及酮形式的N-醣苷胺、1-氨基-1-脱氧-2-酮醣的混合物之后,混合物还将包括不可忽略浓度的未反应伯多胺及碳水化合物。此后,可发生许多产生可广泛描述为类黑精的产物的反应。根据碳水化合物反应物与聚合多胺的身分及反应条件(pH值、温度、氧含量、湿度及添加剂的存在),可选择图1中所示所示反应路径中的一种或多种。此外,获得类黑精产物的有利反应路径可不归类为图1中具体展示的路径中的任一者。
在说明性实施方式中,碳水化合物反应物与伯多胺的重量比在约1:1至约30:1的范围。在另一实施方式中,碳水化合物反应物与伯多胺的重量比在约2:1至约10:1的范围。在另一实施方式中,碳水化合物反应物与伯多胺的重量比在约3:1至约6:1的范围。根据一个方面,固化速率为碳水化合物反应物与伯多胺的重量比的函数。根据此函数,确定随着比率降低,固化速率提高;因此固化时间减少。因此,本发明的一个方面为固化时间与碳水化合物反应物与多胺的重量比直接相关,其限制条件为其他参数保持相当。在另一方面中,当碳水化合物反应物与伯多胺的重量比等于约6:1时,粘合剂固化时间减少至相当的苯酚甲醛粘合剂组合物的固化时间。因此,在一个实施方式中,当碳水化合物反应物与伯多胺的重量比在约2:1至约6:1的范围时,本发明的粘合剂具有超过相当的苯酚甲醛粘合剂系统的固化速率。
如本文所述,反应的另一方面为最初反应物水溶液(其可脱水且用作粘合剂)如上所述具有碱性pH值。本发明的一个方面为碱性粘合剂溶液与酸性溶液相比对金属的腐蚀性较低。因此,克服工业应用的实质性障碍的本发明的一个特征为本文所述的粘合剂由于为碱性粘合剂组合物,所以对可用于制造包括本发明粘合剂的材料的制造设备具有低腐蚀性。本发明优于近来所描述的碳水化合物粘合剂体系(例如美国公开申请第2007/0027283号)的一个区别特征为反应不必经由酸性路径进行。实际上,本发明的一个方面为在导致形成固化粘合剂的化学反应的整个过程中,未固化粘合剂可具有碱性pH值。因此,未固化粘合剂在其整个使用及储存期间不具有腐蚀风险。在说明性实施方式中,固化粘合剂的水性萃取物具有约5至约9范围的pH值。此外,聚合物产物的水性萃取物基本上无色。
在说明性实施方式中,制造以聚合物粘合剂粘合的物质集合体的方法包括:制备含有用于制造聚合物粘合剂的反应物及溶剂的溶液,其中反应物包括碳水化合物反应物及多胺;将溶液置于物质集合体上;使溶剂挥发以形成未固化产品,及使未固化产品经历引起碳水化合物反应物与多胺聚合形成聚合物粘合剂的条件。
在说明性实施方式中,物质集合体包括隔离纤维。在一个实施方式中,纤维绝缘产品描述为包括隔离纤维及粘合剂。如本文中所使用的术语”隔离纤维”指示适于承受高温的耐热性纤维。所述纤维的实例包括(但不限于)矿物纤维(玻璃纤维、渣棉纤维及石棉纤维)、芳酰胺纤维、陶瓷纤维、金属纤维、碳纤维、聚酰亚胺纤维、某些聚酯纤维及人造丝纤维。作为说明,所述纤维基本上不受暴露于高于约120℃的温度的影响。在一个实施方式中,隔离纤维为玻璃纤维。在另一实施方式中,矿物纤维以约70重量%至约99重量%的范围存在。
在说明性实施方式中,物质集合体包括纤维素纤维。举例而言,纤维素纤维可为木刨花、锯屑、木浆或碎木。在另一实施方式中,纤维素纤维可为其它天然纤维,例如黄麻、亚麻、大麻及秸秆。本文中所披露的粘合剂可替代公开的PCT申请WO2008/089847中所描述的粘合剂使用,该案以全文引用的方式并入本文中。在一个实施方式中,披露包含木材颗粒及粘合剂的复合木板。在另一实施方式中,复合木板不含甲醛。在一个实施方式中,复合木板具有大于6mm至13mm的标称厚度范围且具有至少约1050N/mm2的弹性模量(MOE)、至少约7N/mm2的弯曲强度(MOR)及至少0.20N/mm2的内部粘结强度(IB)。在另一实施方式中,复合木板具有大于6mm至13mm的标称厚度范围且具有至少约12.5N/mm2的弯曲强度(MOR)及至少0.28N/mm2的内部粘结强度(IB)。在另一实施方式中,复合木板具有大于6mm至13mm的标称厚度范围且具有至少约1800N/mm2的弹性模量(MOE)、至少约13N/mm2的弯曲强度(MOR)及至少0.40N/mm2的内部粘结强度(IB)。在另一实施方式中,复合木板具有至少约1800N/mm2的弹性模量(MOE)。在另一实施方式中,复合木板具有至少约2500N/mm2的弹性模量(MOE)。在另一实施方式中,复合木板具有至少约14N/mm2的弯曲强度(MOR)。在另一实施方式中,复合木板具有至少约18N/mm2的弯曲强度(MOR)。在一个实施方式中,复合木板具有至少0.28N/mm2的内部粘结强度(IB)。在另一实施方式中,复合木板具有至少0.4N/mm2的内部粘结强度(IB)。在另一实施方式中,在20℃下在水中24小时后,如根据厚度变化所测量,复合木板膨胀小于或等于约12%。在另一实施方式中,在20℃下在水中24小时后,复合木板具有小于或等于约40%的吸水率。
在说明性实施方式中,复合木板为木材颗粒板、定向刨花板或中等密度纤维板。在一个实施方式中,粘合剂占复合木板的约8重量%至约18重量%(干燥树脂的重量比干燥小木块的重量)。在另一实施方式中,复合木板进一步包含蜡。在另一实施方式中,复合木板包含以复合木板的重量计约0.1%至约2%的蜡。在说明性实施方式中,制造以聚合物粘合剂粘合的物质集合体的方法可进一步包括:通过添加一定量的碳水化合物反应物与一定量的伯多胺以使重量比在约2:1至约10:1的范围来制备溶液。在一个实施方式中,制备溶液包括将碳水化合物反应物及多胺添加至水溶液中。在另一实施方式中,制备溶液包括将溶液的pH值调节至约8至约12的范围。在另一实施方式中,制造以聚合物粘合剂粘合的物质集合体的方法可进一步包含将未固化产品封装于适于储存的封装材料中。
在说明性实施方式中,本发明涉及包含物质集合体及粘合剂的组合物;该粘合剂包含碳水化合物反应物与多胺之间反应的聚合物产物,该聚合物产物基本上不溶于水。在一个实施方式中,物质集合体包括矿物纤维、芳酰胺纤维、陶瓷纤维、金属纤维、碳纤维、聚酰亚胺纤维、聚酯纤维、人造丝纤维、玻璃纤维、纤维素纤维或其他颗粒。举例而言,纤维素纤维可包括木刨花、锯屑、木浆和/或碎木。在一个实施方式中,物质集合体包括砂石或其他无机颗粒物质。在一个实施方式中,物质集合体为煤颗粒。在一个实施方式中,碳水化合物反应物选自右旋糖、木糖、果糖、二羟基丙酮及其混合物。在一个实施方式中,多胺选自上文所述的任何多胺。在另一实施方式中,多胺选自二胺、三胺、四胺及五胺。在一个实施方式中,多胺为H2N-Q-NH2,其中Q为烷基、环烷基、杂烷基或环杂烷基。在另一实施方式中,组合物进一步包含含硅化合物。在一个实施方式中,含硅化合物为官能化甲硅烷基醚或官能化烷基甲硅烷基醚,例如氨基官能化烷基甲硅烷基醚。举例而言,在一个实施方式中,含硅化合物可为γ-氨基丙基三乙氧基硅烷、γ-缩水甘油氧基丙基三甲氧基硅烷或氨基乙基氨基丙基三甲氧基硅烷或其混合物。在另一实施方式中,含硅化合物可为氨基官能性低聚硅氧烷。在另一实施方式中,组合物包含选自以下的腐蚀抑制剂:除尘油、磷酸一铵、偏硅酸钠五水合物、三聚氰胺、乙二酸锡(II)及甲基氢聚硅氧烷流体乳液。
在其他说明性实施方式中,粘合剂可置于纤维集合上,基本上脱水,封装,且随后储存或销售至另一方。销售至另一方用于其他制造工艺的未固化产品可称为”装运未固化(ship-outuncured)”。储存用于其他制造工艺的未固化产品可称为”工厂未固化(plantuncured)”。在销售或储存此类型的产品时,其系封装于适合的容器或袋中。
在说明性实施方式中,封装的未固化纤维产品包含未固化粘合剂组合物及纤维集合,其中(i)未固化粘合剂组合物与纤维集合接触从而固结纤维集合,及(ii)将与纤维集合接触的未固化粘合剂组合物封装于适合的封装材料中。在一个实施方式中,未固化粘合剂组合物中水分的量以产品总重量计可在约1重量%至约15重量%的范围。在另一实施方式中,适合封装材料可在环境温度及环境压力下能够将未固化粘合剂组合物中水分的量维持在初始水分含量的约20%以内历时一周时间。在一个实施方式中,不考虑适合封装材料的重量,以封装未固化纤维产品的重量计,封装未固化纤维产品包含约3重量%至约30重量%的未固化粘合剂组合物。在一个实施方式中,不考虑适合封装材料的重量,以封装未固化纤维绝缘产品的重量计,封装未固化纤维产品包含约60重量%至约97重量%的纤维。
本发明的一个方面为本文所述的粘合剂出乎意料地适用于装运未固化应用及工厂未固化应用中。具体而言,装运未固化产品及工厂未固化产品具备未固化粘合剂使得固化可在稍后时间及在稍后位置进行。在装运未固化的情况中,固化温度及时间为对顾客而言具有较大重要性的产品的性质。具体而言,固化温度须足够低以使得产品可使用其现有设备进行固化。此外,固化时间须足够短以使得用于固化产品的周期保持较短。在此行业内,制造设备及可接受的周期已对于包含苯酚甲醛型树脂的未固化产品已确定。因此,足够低的固化温度为适合固化可比苯酚甲醛型产品的固化温度。类似地,足够短的周期为常规用于固化可比苯酚甲醛型产品的周期。本领域技术人员将了解,固化时间及固化温度均不可阐述为明确量,因为特定应用可具有显著不同的参数。然而,应充分了解,模型系统的固化时间及固化温度提供关于基本化学固化反应的动力学的足够代表性信息,使得在各种应用中对粘合剂性能可作出可靠的预测。
在说明性实施方式中,粘合剂的固化时间及固化温度等于或短于(低于)可比苯酚甲醛粘合剂组合物。在一个实施方式中,粘合剂的固化时间短于可比苯酚甲醛粘合剂组合物的固化时间。在另一实施方式中,粘合剂的固化温度低于可比苯酚甲醛粘合剂组合物的固化温度。如本文中所用,可比苯酚甲醛粘合剂组合物如美国专利第6,638,882号所述,该专利在此以全文引用的方式并入本文中。
如以下所论述,可将各种添加剂并入粘合剂组合物中。此类添加剂使本发明的粘合剂具有其他所要特征。举例而言,粘合剂可包括含硅偶联剂。许多含硅偶联剂可购自Dow-CorningCorporation、EvonikIndustries及MomentivePerformanceMaterials。作为说明,含硅偶联剂包括例如甲硅烷基醚及烷基甲硅烷基醚的化合物,其各自可任选被例如卤素、烷氧基、氨基等基团取代。在一个变化形式中,含硅化合物为氨基取代的硅烷,例如γ-氨基丙基三乙氧基硅烷(SILQUESTA-1101;MomentivePerformanceMaterials,CorporateHeadquarters:22CorporateWoodsBoulevard,Albany,NY12211USA)。在另一变化形式中,含硅化合物为氨基取代的硅烷,例如氨基乙基氨基丙基三甲氧基硅烷(DowZ-6020;DowChemical,Midland,MI;USA)。在另一变化形式中,含硅化合物为γ-缩水甘油氧基丙基三甲氧基硅烷(SILQUESTA-187;Momentive)。在另一变化形式中,含硅化合物为氨基官能性低聚硅氧烷(HYDROSIL2627,EvonikIndustries,379InterpacePkwy,Parsippany,NJ07054)。
以溶解的粘合剂固体计,含硅偶联剂通常以约0.1重量%至约1重量%的范围存在于粘合剂中(亦即以添加至水溶液中固体的重量计约0.05%至约3%)。在一应用中,可将一种或多种此类含硅化合物添加至粘合剂水溶液中。随后,将粘合剂涂覆于待粘合材料。此后,必要时可固化粘合剂。此类含聚硅氧化合物增强粘合剂粘着安置有粘合剂的物质(例如玻璃纤维)的能力。增强粘合剂粘着物质的能力提高例如其在非组装或松散组装物质中产生或促进粘着的能力。
在另一说明性实施方式中,本发明的粘合剂可包括一种或多种腐蚀抑制剂。此类腐蚀抑制剂防止或抑制由酸引起的化学分解造成的物质(例如金属)的腐蚀或磨损。当本发明的粘合剂中包括腐蚀抑制剂时,粘合剂的腐蚀性与不存在抑制剂的粘合剂的腐蚀性相比降低。在一个实施方式中,可利用此类腐蚀抑制剂来降低本文所述含矿物纤维组合物的腐蚀性。作为说明,腐蚀抑制剂包括以下中的一种或多种:除尘油或磷酸一铵、偏硅酸钠五水合物、三聚氰胺、乙二酸锡(II)和/或甲基氢聚硅氧烷流体乳液。当包括于本发明的粘合剂中时,以溶解的粘合剂固体计,腐蚀抑制剂通常以约0.5重量%至约2重量%的范围存在于粘合剂中。本发明的一个方面为粘合剂溶液的碱性及基本上脱水的未固化粘合剂使得对腐蚀抑制添加剂的需要大为降低。在一个实施方式中,粘合剂不含腐蚀抑制剂且粘合剂溶液的腐蚀性在可接受的范围。
在说明性实施方式中,粘合剂可进一步包括非水性保湿剂。非水性保湿剂可包括一种或多种聚醚。举例而言,非水性保湿剂可包括具有直链和/或分支链烷基及烷芳基的环氧乙烷或环氧丙烷缩合物。在一个实施方式中,非水性保湿剂包括聚乙二醇、聚丙二醇醚、硫醚、聚氧亚烷基二醇(例如Jeffox)、二丙二醇和/或聚丙二醇(例如Pluriol或Pluriol)。在一个实施方式中,非水性保湿剂包含聚氧亚烷基二醇或聚丙二醇。在另一实施方式中,非水性保湿剂包括基于多羟基化合物的化合物(例如部分或完全酯化的多羟基化合物)。在另一实施方式中,非水性保湿剂包括基于甘油、丙二醇、乙二醇、乙酸甘油酯、山梨糖醇、木糖醇或麦芽糖醇的多羟基化合物。
在另一实施方式中,非水性保湿剂包括基于四氢呋喃、己内酯和/或具有含约7个至约18个碳原子的烷基且具有约4个至约240个亚乙基氧基单元的烷基苯氧基聚(亚乙基氧基)乙醇的具有多个羟基的化合物。举例而言,非水性保湿剂可包括庚基苯氧基聚(亚乙基氧基)乙醇和/或壬基苯氧基聚(亚乙基氧基)乙醇。在另一实施方式中,非水性保湿剂包括己醣醇(例如脱水山梨糖醇、山梨糖醇酐、一缩甘露糖醇和/或二缩甘露糖醇)的聚氧亚烷基衍生物。在另一实施方式中,非水性保湿剂可包括部分长链脂肪酸酯,例如脱水山梨糖醇单月桂酸酯、脱水山梨糖醇单棕榈酸酯、脱水山梨糖醇单硬脂酸酯、脱水山梨糖醇三硬脂酸酯、脱水山梨糖醇单油酸酯和/或脱水山梨糖醇三油酸酯的聚氧亚烷基衍生物。
在说明性实施方式中,非水性保湿剂包括环氧乙烷与疏水性基材的缩合物,该基材通过使环氧丙烷与丙二醇缩合而形成。在一个实施方式中,非水性保湿剂包括含硫缩合物,例如通过使环氧乙烷与高碳烷基硫醇(例如壬基、十二烷基、十四烷基硫醇或烷基中具有约6个至约15个碳原子的烷基硫酚)所制备的。在另一实施方式中,非水性保湿剂包括长链羧酸(例如月桂酸、肉豆蔻酸、棕榈酸或油酸)的环氧乙烷衍生物。在另一实施方式中,非水性保湿剂包括长链醇(例如辛醇、癸醇、月桂醇或鲸蜡醇)的环氧乙烷衍生物。在另一实施方式中,非水性保湿剂包括环氧乙烷/四氢呋喃共聚物或环氧乙烷/环氧丙烷共聚物。
以下实施例更详细说明特定实施方式。此类实施例仅出于说明的目的而提供,且不应以任何方式解释为将本发明或本发明的概念限于任何特定实体组态。
实施例
实施例1:将50g右旋糖(0.278mol)、50g己二胺(0.431mol)溶解于566.6g去离子水中的溶液(15%固体溶液,pH11.9)加热至溶液的沸点。观察到淡褐色水不溶性聚合物在反应容器中沉淀。
实施例2:自以上50g右旋糖(0.278mol)、50g己二胺(0.431mol)溶解于566.6g去离子水中的溶液(15%固体溶液,pH11.9),将2g粘合剂溶液涂覆于置放于测湿度天平(MoistureBalance)中的过滤垫上且在120℃下加热15分钟。在过滤垫上形成淡褐色水不溶性聚合物。使用100g去离子水萃取固化过滤垫的萃取物基本上无色且具有6.8的pH值。
实施例3:制备85g右旋糖(0.472mol)、15g己二胺(0.129mol)溶解于566.6g去离子水中的溶液(15%固体溶液,pH10.8)。将2g粘合剂溶液涂覆于置放于测湿度天平中的过滤垫上且在140℃下加热15分钟。在过滤垫上形成淡褐色水不溶性聚合物。使用100g去离子水萃取固化过滤垫的萃取物基本上无色且具有6.8的pH值。
实施例4:制备95g右旋糖(0.528mol)、5g己二胺(0.043mol)溶解于566.6g去离子水中的溶液(5%固体溶液)。将2g粘合剂溶液涂覆于置放于测湿度天平中的过滤垫上且在180℃下加热15分钟。在过滤垫上形成淡褐色水不溶性聚合物。使用100g去离子水萃取固化过滤垫的萃取物基本上无色且具有6.8的pH值。
比较例1:制备180g右旋糖(1mol)溶解于1020g去离子水中的溶液(15%固体溶液)。将2g粘合剂溶液涂覆于置放于测湿度天平中的过滤垫上且在180℃下加热15分钟。过滤垫上未形成水不溶性聚合物。所得经热处理的粘合剂基本上完全可溶于水。
固化速率及固化时间:以含有15%固体的粘合剂浸渍重量为44g的正方形玻璃纤维毡片(13”×13”)(相当于34.5g/ft2)。通过真空抽吸移除过量粘合剂,且将潮湿毡片在烘箱中在90℉下干燥至少12小时(再循环)。
将干燥毡片切割为四个相同尺寸的正方形。将正方形堆叠在彼此之上,且至少一个与记录器(即ovenmole)连接的热电偶置放于第二层与第三层之间的堆叠体中间。
将具有温度控制压板的模压机加热至400℉(204℃)。配备有热电偶的样品置于压板中间,且挤压至5/8”的厚度维持预定时间(即3.5分钟、4.0分钟、5.0分钟、6.0分钟、15分钟)。
通过测试表面均匀度、防水性及萃取物来评估各模制样品的固化度。当表面平滑而无任何”凸块”,样品在浸入水中时并不显著弱化及样品浸入于水中时未形成明显萃取物颜色时,样品视为固化。在模制循环期间测量样品中心的温度特征且展示于图3中。
比较例2:苯酚甲醛粘合剂。
以干燥固体计的组成:
-2.41份硫酸铵
-1.08份氨
-0.21份硅烷A1101
-96.3%苯酚甲醛树脂:脲预混物(70:30)
在图3中比较例2称为粘合剂1。
比较例3:碳水化合物-无机酸粘合剂。
以干燥固体计的组成:
-81.59份右旋糖
-17.09份硫酸铵
-1份氨
-0.3份硅烷A1101
在图3中比较例3称为粘合剂2。
实施例5:
以干燥固体计的组成:
-80.94份右旋糖及氨溶液(含有2摩尔/升右旋糖及2摩尔/升氨的水溶液)
-19.06份己二胺
在图3中实施例5称为粘合剂4。
经测定本发明范畴内的粘合剂实现充分固化所需的时间少于3个具有不同化学性质的比较例粘合剂系统的时间。此模型系统说明只要其他变量保持恒定,固化时间取决于粘合剂系统的化学性质。本发明范畴内的说明性粘合剂组合物的化学性质与此类其他例示性系统相比实现改进的固化时间。结果展示如下:
粘合剂 | 实现完全固化的模制时间 |
比较例2-粘合剂1 | 最少240秒 |
比较例3-粘合剂2 | 最少300秒 |
实施例5-粘合剂4 | 在210秒时固化 |
现参照图3,展示粘合剂1、粘合剂2及粘合剂4各自特有的温度特性。应注意温度分布为各粘合剂所特有。尚未确定固化速率及固化时间不为固化温度分布的特征。然而,固化温度分布有助于了解及预测固化速率及固化时间。具体而言,比较例3需要最长的固化时间且类似地固化温度分布需要最大量时间来逼近最大值。类似地,实施例5需要最少量的时间来逼近最大值且显示最短的固化时间。
碳水化合物反应物:多胺比率对固化周期的影响。用不同比率的右旋糖单水合物(DMH)与己二胺(HMDA)制备湿式布层毡片(WLM)。所测试的重量比分别包括75/25、85/15及92/8。
将15%右旋糖-HMDA粘合剂涂覆于5个WLM上。制备以下粘合剂组合物:
制备厚度为3/8"的13"×13"块状毡片。用于模制毡片的压机设定为400℉。模制样品后,其厚约5/8"。首先以15分钟时间间隔测定温度分布。下一样品挤压4分钟;此为固化可比苯酚甲醛粘合剂组合物所耗费的时间(结果未图示)。以不同固化时间重复实验,直至确定固化各组合物所需的最短时间。基于重量测定各粘合剂的固化程度。测得以下结果:
如上所述,基于苯酚甲醛的相当产品(例如比较例2)以4分钟周期固化。此外,基于碳水化合物的相当粘合剂(例如比较例3)以5分钟周期固化。此类结果指示本发明范畴内具有85/15或低于85/15比率的碳水化合物反应物与第一多胺的粘合剂与基于苯酚甲醛的产品相比以可比或较快的速率固化。其他实验显示在具有较短固化时间的产品中固化温度可降低,从而在较低温度下实现相等固化时间。所得结果与基于阿伦尼乌斯方程所得到的期望值大体一致。
除详细描述的那些实施例外,还进行以下实施例以确保碳水化合物反应物及多胺可包含广泛替代物。
其他右旋糖-多胺实施例:
实施例16:以11NHCl将56.08g去离子水、7.15g右旋糖单水合物及3.5g1,12-二氨基十二烷的悬浮液酸化至pH1.0,且在搅动下加热至70℃,产生澄清无色溶液。溶液在160℃下形成热固性水不溶性聚合物。(测试条件:将2g粘合剂溶液涂覆于置放于测湿度天平中的过滤垫上。过滤垫在160℃下加热15分钟。)用100g去离子水萃取固化过滤垫的萃取物基本上无色。
实施例17:8.25g右旋糖单水合物及2.50g1,5-二氨基-2-甲基戊烷(DytekA,Invista)溶解于56.08g去离子水中的溶液在160℃下形成热固性水不溶性聚合物。(测试条件:将2g粘合剂溶液涂覆于置放于测湿度天平中的过滤垫上。过滤垫在160℃下加热15分钟。)用100g去离子水萃取固化过滤垫的萃取物基本上无色。
实施例18:8.03g右旋糖单水合物及2.70gN-(3-氨基丙基)-1,3-丙二胺溶解于56.08g去离子水中的溶液在200℃下形成热固性水不溶性聚合物。(测试条件:将2g粘合剂溶液涂覆于置放于测湿度天平中的过滤垫上。过滤垫在200℃下加热15分钟。)用100g去离子水萃取固化过滤垫的萃取物具有微带浅黄色的颜色。
实施例19:制备1.0g右旋糖(5.55mmol)、1.0g(约2.27mmol)JeffamineT-403聚醚胺溶解于8.5g去离子水中的溶液(19%固体溶液)。将2g粘合剂溶液涂覆于置放于测湿度天平中的过滤垫上且在180℃下加热5分钟。在过滤垫上形成淡褐色水不溶性聚合物。使用100g去离子水萃取固化过滤垫的萃取物基本上无色且具有7.1的pH值。
JeffamineT-403聚醚胺为平均分子量为440的三官能性伯胺。其氨基位于脂族聚醚链末端的仲碳原子上。其结构可表示如下,其中x、y及z的总和为6:
以气体热解分析粘合剂样品的工序。将约10g上面具有粘合剂的固化产品置于试管中,随后将该试管加热至1000℉维持2.5分钟,此时在顶空进行取样且利用气相层析/质谱分析(GC/MS)在以下条件下进行分析:烘箱,50℃维持1分钟-10℃/分钟至300℃维持10分钟;入口,280℃无分流;管柱,HP-530mm×0.32mm×0.25μm;柱流速,1.11毫升/分钟氦;侦测器,MSD280℃;注射体积,1mL;检测器模式,扫描34amu-700amu;阀值,50;及采样率,22次扫描/秒。针对质谱的威利文库(Wileylibrary)计算机搜寻样品中层析峰的质谱。报导最佳匹配。产生范围为0至99的质量指数(与文库光谱匹配的接近度)。仅报导质量指数大于或等于90的峰的身分。
下表提供预期来自热解基于类黑精的粘合剂组合物期间所产生气态化合物的GC/MS分析的代表性热解资料。
以下为在使用己二胺作为多胺组分制备的粘合剂样品的热解气相色谱分析(PyGC-MS)中所观测到的物质的清单。热解在200℃、300℃及770℃下进行。指纹图谱显示在200℃及300℃下质谱层析图中对应于乙酸的极明显峰,未见于使用右旋糖及硫酸铵制备的样品(参见比较例3)中,其中明显挥发物为SO2,尤其在300℃下。在770℃下,所观测到的峰按照滞留时间递增次序指定如下:A:共洗脱C5H10、C5H12、丙酮、可能的低分子量乙酸酯;B:C5H8二烯;C:C5H8二烯;D:可能为戊醇;E:C6H12-甲基戊烯;F:己烷;G:甲基环戊烷;H:环己二烯;I:C6H10-可能为甲基环戊烷;J:苯;K:乙酸;L:环己烯;M:可能为壬醇;N:2-甲基-3-戊酮;O:2,5-二甲基呋喃;P:C7H10+未指定共洗脱;Q:吡啶+未指定共洗脱剂;R:甲苯;S:可能为癸烯醛+未指定共洗脱剂;T:2-乙基-5-甲基呋喃;U:甲基吡啶;V:甲基吡咯;W:二甲苯;X:未指定-具有醇官能基;Y:未指定;Z:二甲苯+未指定共洗脱剂;AA:未指定;AB:二甲基吡咯;AC:二甲基吡啶;AD:二甲基吡啶;AE:未指定;AF:未指定;AG:乙基甲基吡咯+未指定共洗脱剂;AI:未指定但质谱不同(含N),与吡咯相关;AJ:未指定但质谱不同(含N),可能为乙酰胺;AK:未指定但质谱不同(含N),与吡咯相关;AL:未指定但质谱不同(含N),与吡咯相关;AM:未指定但质谱不同(含N),与吡咯相关。由峰AI至峰AM所见的不同质谱未见于不具有多胺组分的先前粘合剂的资料中。
评估干燥及风化拉伸强度的工序。当评估其干燥及”风化”拉伸强度时,以指定粘合剂制备的含玻璃珠粒的壳骨(shellbone)组合物分别提供以该特定粘合剂制备的玻璃纤维产品的可能拉伸强度及可能耐久性的指示。预测的耐久性系基于壳骨的风化拉伸强度:干燥拉伸强度比率。制备壳骨,风化,且如下进行测试,例如测试己二胺-右旋糖粘合剂混合物。
将壳骨模具(迪塔特铸件测试设备(DietertFoundryTestingEquipment);热外壳固化附件(HeatedShellCuringAccessory),366型,及外壳模具附件(ShellMoldAccessory))设定为所需温度(一般为425℉),且加热至少一个小时。加热壳骨模具的同时,制备约100g粘合剂水溶液(一般含15%粘合剂固体)(例如如实施例7中所述)。使用大玻璃烧杯,减差称量727.5g玻璃珠粒(QualityBallotiniImpactBeads,规格AD,美国筛70-140、106-212微米-#7,来自PottersIndustries,Inc)。将玻璃珠粒倾入干净且干燥的混合碗中,该碗安放于电力混合器台架上。将约75g粘合剂水溶液缓慢倾至混合碗中的玻璃珠粒中。随后开启电力混合器且搅动玻璃珠粒/粘合剂混合物一分钟。使用大抹刀,刮削搅拌器(混合器)的侧面以移除任何粘合剂块,同时亦刮削边缘,其中玻璃珠粒处于碗的底部。随后再开启混合器一分钟,且随后自单元移除搅拌器(混合器),继而移除含有玻璃珠粒/粘合剂混合物的混合碗。使用大抹刀,尽可能移除粘附于搅拌器(混合器)的粘合剂及玻璃珠粒,且随后搅拌至混合碗中的玻璃珠粒/粘合剂混合物中。随后刮削碗的侧面以混合任何可能已积聚在侧面上的过量粘合剂。此时,玻璃珠粒/己二胺-右旋糖粘合剂混合物准备就绪备用于在壳骨模具中进行模制。
确认壳骨模具的载片在底部模具压板内对准。随后使用大抹刀,将玻璃珠粒/己二胺-右旋糖粘合剂混合物迅速添加至壳骨模具内的三个模具腔中。抹平各腔中混合物的表面,同时刮除过量混合物以使壳骨具有均一表面积。以额外玻璃珠粒/己二胺-右旋糖粘合剂混合物填充存在于任何腔中的任何不一致或间隙,且随后抹平。玻璃珠粒/己二胺-右旋糖粘合剂混合物置放于壳骨腔中且混合物暴露于热量后,即开始固化。因为操作时间可影响测试结果,例如可能产生具有两个不同固化层的壳骨;所以一致且迅速地制备壳骨。若壳骨模具已填满,则将顶部压板快速置放于底部压板上。同时或其后快速通过马表开始测量固化时间,在此期间底部压板的固化温度在约400℉至约430℉范围内,而顶部压板的温度在约440℉至约470℉范围内。历时七分钟时间后,移除顶部压板且抽出载片以便可移除所有三个壳骨。随后将新制成的壳骨置于线架上,与壳骨模具压板相邻,且冷却至室温。此后,各壳骨进行标记且个别置放于适当标记的塑料储存袋中。若壳骨在其制备当天不能测试,则将含有壳骨的塑料袋置放于干燥器单元中。
壳骨的条件处理(风化)工序:开启BlueM潮湿箱,且随后设置为提供90℉及90%相对湿度(亦即90℉/90%rH)的风化条件。检查潮湿箱侧面上的水箱且定期加满,通常每次将其开启。允许潮湿箱在至少4小时时间内达到指定风化条件,具有典型的全天平衡期。经由敞开的潮湿箱门将待风化的壳骨一次一个快速装载(因为当门敞开时,湿度及温度均降低)于潮湿箱的上部开槽支架上。记录下壳骨置放于潮湿箱中的时间,且进行24小时时期的风化。此后,打开潮湿箱门且将一组壳骨一次快速移出且个别置于相应塑料储存袋中,完全密封。一般而言,如上所述一次风化一至四组壳骨。风化的壳骨即刻带入英氏室(Instronroom)中且进行测试。
破坏壳骨的测试工序:在英氏室中,壳骨测试法装载于5500R英氏机上同时确保安装正确测力计(亦即静态测力计5kN),且使机器升温十五分钟。在此期间,验证壳骨测试夹具安装于机器上。使测力计归零且平衡,且随后如下一次测试一组壳骨:自塑料储存袋中移出壳骨且随后称重。随后将重量(以克为单位)输入与英氏机相关联的计算机中。随后将所测得的壳骨厚度(以英寸为单位)作为试样厚度在与英氏机相关联的计算机中输入三次。随后将壳骨试样置放于英氏机的夹具中,且经由英氏机上的小键盘引发测试。移除壳骨试样后,将所测得的破坏点输入与英氏机相关联的计算机中,且持续测试直至组中所有壳骨均进行了测试。
碳水化合物反应物:多胺比率对壳骨性质的影响。用不同比率的右旋糖单水合物(DMH)与己二胺(HMDA)以及硅烷添加剂(ISIO200)制备壳骨,如上所述在25mm/min的测试速度下进行检验。所测试的重量比率分别包括90/10、85/15、80/20及75/25。
实施例:玻璃棉(玻璃纤维)试验
根据在玻璃棉产品(Ac+032100mm1200mm宽度;32kg/m3-15m/min)上的固化及刚性通过测量分离强度及密度对两种葡萄糖-己二胺粘合剂与标准粘合剂的质量进行比较。
粘合剂1:85%葡萄糖-15%己二胺。
粘合剂2:90%葡萄糖-10%己二胺。
普通分离强度(高压釜前)及风化分离强度(高压釜后)可如国际专利申请公开第WO2008/089851号或第WO2009/019235号中所述进行测量。
标准粘合剂的分离强度:
粘合剂1的分离强度:
粘合剂2的分离强度:
在试验期间观察到:产品在具有两种葡萄糖-己二胺粘合剂的在线棕色更深。
结论:利用两种葡萄糖-己二胺粘合剂时,分离强度(其为纵向拉伸强度)结果显示明显改进;且在三次其他刚性测试(“60°”测试-以60°抵靠滑槽倾斜时测量的下垂;”桌面”测试-抵靠水平面测量的下垂;及Acermi测试-离桌面边缘35cm测量的下垂)中观察到明显改进。
实施例:颗粒板试验
在以下条件下对使用脲-甲醛粘合剂(UFE0)与使用碳水化合物多胺(己二胺)粘合剂制成的颗粒板的质量进行比较。
板尺寸:350mm×333mm及主要10mm厚(2×20mm)
压板温度:主要为195℃但也为175℃及约215℃。
压力:引述为3.5Mpa(35巴)-实际35Kg/cm2,以56巴实现。
密度目标:650kg/m3。
挤压前制备预成形物。
结果:
粘合剂 | 挤压时间 | IB强度 |
(秒) | (Mpa) | |
UF E0 | 150 | 0.75 |
100 | 0.69 | |
80 | 0.66 | |
碳水化合物多胺 | 300 | 0.92 |
240 | 0.99 | |
180 | 0.88 | |
150 | 0.73 | |
120 | 0.68 | |
90 | 0.15 |
所制备的所有板均表现高质量;未观察到分裂或脱气。用此碳水化合物多胺制剂制成的板在其固化150秒时与脲甲醛板相当。
Claims (40)
1.一种制造包含以固化的、基本上不溶于水的、不含甲醛的热固性聚合物粘合剂粘合的纤维素纤维的复合木板的方法,
所述粘合剂包含碳水化合物反应物与多胺的聚合物产物,
其中所述复合木板选自:具有至少1800N/mm2的弹性模量(MOE)的复合木板;具有至少18N/mm2的弯曲强度(MOR)的复合木板;具有至少0.28N/mm2的内部粘结强度(IB)的复合木板;在20℃下在水中24小时后根据厚度变化测量的膨胀小于或等于12%的复合木板;在20℃下在水中24小时后具有小于或等于40%的吸水率的复合木板;包含蜡的复合木板;定向刨花板;和中等密度纤维板,
其中所述碳水化合物反应物为还原糖,所述多胺为伯多胺H2N-Q-NH2,其中Q为烷基、环烷基、杂烷基或环杂烷基,其各自任选被取代且条件是伯多胺不由聚亚乙基亚胺组成;
该固化的粘合剂是固化粘合剂反应物的产物;
其中使粘合剂反应物固化以形成固化的、基本上不溶于水的、不含甲醛的热固性聚合物粘合剂包括使所述粘合剂反应物暴露于热以引发粘合剂中的化学变化,使得水释放。
2.根据权利要求1的方法,其中不使用苯酚作为用于粘合剂的试剂。
3.根据权利要求1或2的方法,其中碳水化合物反应物为所述粘合剂的主要反应物。
4.根据权利要求1或2的方法,其中所述粘合剂反应物存在于水溶液中。
5.根据权利要求1或2的方法,其中该纤维素纤维选自木刨花、锯屑、木浆和碎木。
6.根据权利要求1或2的方法,其中该还原糖选自右旋糖、木糖、果糖及其混合物。
7.根据权利要求1或2的方法,其中多胺为选自二胺、三胺、四胺及五胺的伯多胺。
8.根据权利要求1或2的方法,其中Q为选自C2至C24的烷基。
9.根据权利要求1或2的方法,其中Q为选自C2至C8的烷基。
10.根据权利要求1或2的方法,其中Q为选自C3至C7的烷基。
11.根据权利要求1或2的方法,其中Q为C6的烷基。
12.根据权利要求1或2的方法,其中Q选自环己基、环戊基及环丁基。
13.根据权利要求1或2的方法,其中该多胺为选自1,6-二氨基己烷及1,5-二氨基-2-甲基戊烷的二胺。
14.根据权利要求1或2的方法,其中该二胺为1,6-二氨基己烷。
15.根据权利要求1或2的方法,其中该多胺为选自二亚乙基三胺、及双(六亚甲基)三胺的三胺。
16.根据权利要求1或2的方法,其中该多胺为三亚乙基四胺。
17.根据权利要求1或2的方法,其中该多胺为四亚乙基五胺。
18.根据权利要求1或2的方法,其中该多胺为聚醚-多胺。
19.根据权利要求18的方法,其中该聚醚-多胺为二胺或三胺。
20.根据权利要求1或2的方法,其中该还原糖与该伯多胺的重量比在1:1至30:1的范围。
21.根据权利要求1或2的方法,其中该还原糖与该伯多胺的重量比在2:1至10:1的范围。
22.根据权利要求1或2的方法,其中还原糖与伯多胺的重量比范围在3:1-6:1。
23.根据权利要求4的方法,其中反应物水溶液具有碱性pH。
24.根据权利要求1或2的方法,其中该聚合物粘合剂强烈吸收420nm的光。
25.一种包含以固化的、基本上不溶于水的、不含甲醛的热固性聚合物粘合剂粘合的纤维素纤维的复合木板,
所述粘合剂包含碳水化合物反应物与多胺的聚合物产物,
其中所述复合木板选自:具有至少1800N/mm2的弹性模量(MOE)的复合木板;具有至少18N/mm2的弯曲强度(MOR)的复合木板;具有至少0.28N/mm2的内部粘结强度(IB)的复合木板;在20℃下在水中24小时后根据厚度变化测量的膨胀小于或等于12%的复合木板;在20℃下在水中24小时后具有小于或等于40%的吸水率的复合木板;包含蜡的复合木板;定向刨花板;和中等密度纤维板,
其中所述碳水化合物反应物为还原糖,所述多胺为伯多胺H2N-Q-NH2,其中Q为烷基、环烷基、杂烷基或环杂烷基,其各自任选被取代且条件是伯多胺不由聚亚乙基亚胺组成,
其中该固化的粘合剂是固化粘合剂反应物的产物,从而通过使所述粘合剂反应物暴露于热以引发粘合剂中的化学变化,使得水释放,来阐述固化的、基本上不溶于水的、不含甲醛的热固性聚合物粘合剂。
26.根据权利要求25的复合木板,其中不使用苯酚作为试剂。
27.根据权利要求25或26的复合木板,其中碳水化合物反应物为所述粘合剂的主要反应物。
28.根据权利要求25或26的复合木板,其中所述粘合剂反应物存在于水溶液中。
29.根据权利要求25或26的复合木板,其中该纤维素纤维选自木刨花、锯屑、木浆及碎木。
30.根据权利要求25或26的复合木板,其中该还原糖选自右旋糖、木糖、果糖及其混合物。
31.根据权利要求25或26的复合木板,其中该多胺选自二胺、三胺、四胺及五胺。
32.根据权利要求25或26的复合木板,其中所述多胺为1,6-二氨基己烷。
33.根据权利要求25或26的复合木板,其中该复合木板包含蜡。
34.根据权利要求25或26的复合木板,其中该复合木板具有至少1800N/mm2的弹性模量(MOE)。
35.根据权利要求25或26的复合木板,其中该复合木板具有至少18N/mm2的弯曲强度(MOR)。
36.根据权利要求25或26的复合木板,其中该复合木板具有至少0.28N/mm2的内部粘结强度(IB)。
37.根据权利要求25或26的复合木板,其中该复合木板在20℃下在水中24小时后根据厚度变化所测量的膨胀小于或等于12%。
38.根据权利要求25或26的复合木板,其中该组合物为复合木板且它在20℃下在水中24小时后具有小于或等于40%的吸水率。
39.根据权利要求25或26的复合木板,其中该复合木板为定向刨花板或中等密度纤维板。
40.根据权利要求25或26的复合木板,其中该复合木板为颗粒板。
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