CN103403122A - 低 ph、大豆粉非脲稀释剂及其制备方法 - Google Patents
低 ph、大豆粉非脲稀释剂及其制备方法 Download PDFInfo
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- CN103403122A CN103403122A CN201280009196XA CN201280009196A CN103403122A CN 103403122 A CN103403122 A CN 103403122A CN 201280009196X A CN201280009196X A CN 201280009196XA CN 201280009196 A CN201280009196 A CN 201280009196A CN 103403122 A CN103403122 A CN 103403122A
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Abstract
本发明提供一种具有非脲稀释剂的改进的大豆组合物,其pH小于5.0,具有改进的粘度稳定性和优异的湿和干强度,更有效的生产和更低的生产成本。任选地,该组合物还可以包括将交联剂、另外的稀释剂或者二者加入到该大豆非脲稀释剂粘合剂中和/或加入乳化的或分散的聚合物。
Description
本申请要求2012年2月17日申请的临时申请号US61/443841的权益,其整个内容在此通过引用加入。
发明领域
本发明提供组合物和通过将基于非脲的稀释剂与大豆粉组合,并且将pH降低到小于5来制造粘合剂的方法。
发明背景
衍生自含蛋白质的大豆粉的粘合剂首先在二十世纪二十年代获得了全面使用(参见例如US专利1813387,1724695和1994050)。适用于粘合剂中的大豆粉过去和现在仍然是如下来获得的:从大豆中除去一些或者大部分的油,产生了残留的大豆粗粉,其随后研磨成极细的大豆粉。典型的,使用己烷来从压碎的大豆中提取大部分的非极性油,虽然挤出/萃取方法也是合适的除油手段。
所形成的大豆粉通常然后用碱试剂变性(即,将蛋白质的第二、第三和/或第四结构改变来暴露能够键合的另外的极性官能团),并且水解到一定程度(即,断开共价键)来产生用于在干燥条件下木材粘合的粘合剂。但是,这些早期的大豆粘合剂表现出差的耐水性,这将它们的用途严格限制到内部应用。此外,它们的固体非常低,典型的小于20%,并且经常是非常稠的和不可喷涂的。
在二十世纪二十年代,首先开发了酚-甲醛(PF)和脲-甲醛(UF)粘合剂树脂。酚-甲醛和三聚氰胺改性的脲-甲醛树脂是外部耐久的,但是具有高的原料成本,其最初限制了它们的用途。第二次世界大战导致快速开发了用于耐水和耐候应用包括外部应用的这些粘合剂。但是,基于蛋白质的粘合剂,主要是基于大豆粘合剂(其经常与血液或者其他蛋白质组合)被继续用于许多内部应用中。
目前,内部层合板、中密度纤维板(MDF)和颗粒板(PB)主要是使用脲-甲醛(UF)树脂来生产的。后两者需要低粘度/可喷涂粘合剂体系来在商业上可行。虽然非常结实、快速固化和相当容易使用,但是这些UF树脂缺乏沿着聚合物主链的水解稳定性。这导致显著量的游离甲醛从最终产品中释放出来(和最终被家里的居住者吸入)。已经有几个立法行动来推进当用于家庭内应用时降低甲醛的排放(Health and Safety Code Title17CaliforniaCode of Regulations Sec.93120-93120.12,和the2010United States“Formaldehyde Standards for Composite Wood Products Act”。
外部级板例如层合板和定向条板(OSB)最经常的是用酚甲醛或者聚合的亚甲基二苯基二异氰酸酯(pMDI)粘合剂来生产的。对于OSB,该应用需要低粘度粘合剂,使它适于喷涂,最经常地经由旋转式圆盘雾化器来施用。
基于大豆的粘合剂可以使用大豆粉、大豆蛋白质浓缩物(SPC)或者大豆蛋白质分离物(SPI)作为起始材料。为了简化,本发明将包含大于20%的碳水化合物的全部大豆产品称为“大豆粉”。大豆粉没有SPI昂贵,但是也包含大量的碳水化合物,需要更复杂的交联技术,因为交联导致了基于大豆的粘合剂明显改进的耐水性。
SPC包含了比大豆粉更大量的蛋白质,但是包含比SPI更少的蛋白质。典型的,SPC是使用醇清洗来除去可溶性碳水化合物来生产的。
SPI典型地是通过等电位沉淀方法来生产的。这种方法不仅除去了可溶性糖,而且除去了可溶性更大的低分子量蛋白质,留下主要是高分子量蛋白质,其对于粘合性而言是最佳的,甚至没有改性时也是如此。结果,SPI产生了非常强的粘合剂,其具有可感知的耐久性。但是,SPI是相当昂贵的,因此不是基于大豆的粘合剂理想的大豆来源。基于SPI的粘合剂还具有非常低的固体,并且这导致了垫子中不可接受水平的湿气。因此,非常需要由大豆粉来生产高品质粘合剂,其是高固体的,并且粘度仍然足够低,来允许使用通常的喷涂技术。
Li等人(Li)的US专利7252735描述了用聚酰胺-胺表氯醇来源的树脂(PAE)交联的大豆蛋白质。Li描述了这些具体的PAE,其是用于纸张的已知的湿强添加剂,与蛋白质官能团发生许多可能的反应。在Li中,SPI是用碱在温暖的温度变性的,然后与合适的PAE树脂组合来产生耐水的键合。Li没有使用非脲稀释剂,他也没有认识到小于5的pH对于大豆-PAE的长期稳定性的重要性。
Wescott的US专利No.7345136描述了一种在制剂中碱变性大豆粉的方法,该制剂用于通过直接加入甲醛和酚的共聚中。该体系的pH然后降低到<5的水平。这样的方法如果用于本发明,将导致非常高的粘度和低的固体,这是过度碱变性步骤的结果;使得将该粘合剂用于PB、MDF或OSB应用显得不切实际。或者,如果将这个发明的方法用于Wescott方法(7345136),则当甲醛加入大豆粉中时,实现了立即凝胶化。这是该方法不足的变性水平的结果。显然,本发明是明显不同于前述这些的大豆构造。
Brady在US专利申请系列号12/287394中揭示了稀释剂可以与大豆粉和某些交联剂一起使用来产生低粘度粘合剂,但是Brady教导了“pH典型的范围是5-10”。在本发明中,pH总是小于5。较低的pH对于大豆粉和某些交联剂如聚合的亚甲基二苯基二异氰酸酯(pMDI)和PAE之间足够的稳定性而言是关键的。
发明内容
本发明提供组合物和通过将非脲稀释剂和大豆粉组合(pH小于5)来制造粘合剂的方法,来生产商业可行的粘合剂。本发明中的术语“稀释剂”表示能够产生具有大豆粉的均匀混合物的任何非脲稀释剂。
在本发明的一种实施方案中,大豆粉分散在水和非脲稀释剂混合物中,并且pH降低到pH小于5.0,优选小于4.5,但是大于2.0,并且搅拌至少1分钟。不包括任何另外的交联,这将产生稳定的大豆-稀释剂产物。
最终粘合剂组合物的pH(加入交联剂或者没有加入交联剂)可以是2-5。优选3.5-4.5。典型的,调整该pH来控制最终粘合剂的反应速率或稳定性。任何合适的酸或者碱可以用于改变pH。
该制备方法典型地在室温进行,但是在5-50℃间的任何温度进行该方法都是合理的。
该低pH的大豆-稀释剂粘合剂可以进一步包括交联剂、乳化的聚合物、另外的稀释剂或者其任意组合。这些添加剂用于改变最终粘合剂的干或湿强度、流变性或者物理性能。
附图说明
图1是实施例2的干强度结果。
图2是实施例2的湿强度结果。
图3是实施例3和4的粘度结果,(L)表示低pH(<5)和H表示高pH(>5)。
图4是实施例5-4和6-4随时间变化的粘度结果。
具体实施方式
在说明书和权利要求书中,术语“包括”和“包含”是开放式术语,并且应当解释为表示“包括但不限于…”。这些术语包括更大限制性的术语“基本由…组成”和“由…组成”。
作为此处和附加的权利要求书中所使用的,单数形式“一个”、“一种”和“该”包括复数指代,除非上下文另有明确指示。同样,术语“一个”(或者“一种”),“一种或多种”和“至少一种”可以在此互换使用。还要注意的是术语“包含”、“包括”、“特征为”和“具有”可以互换使用。
除非另有定义,否则此处所用的科技术语具有本发明所属领域的技术人员通常所理解的相同的含义。在此明确提及的所有出版物和专利通过引用将它们全部加入,以为了包括描述和公开化学品、仪器、统计分析和方法(其报道在所述公开文献中,其可能用于本发明)的全部目的。本说明书中全部引用的参考文献是根据本领域技术人员的水平来采取的。在本文中没有内容被解释为认为本发明早于本发明现有技术的这些公开文献。
本发明提供一种通过如下得到的新粘合剂,将非脲稀释剂与大豆粉组合,并且将pH降低到小于5。该稀释剂可以加入到大豆粉水混合物中或者该大豆粉可以加入到水-稀释剂混合物中。
术语“稀释剂”表示描述了任何非脲添加剂,其可以加入到大豆粉中,并且产生均匀的混合物。在优选的实施方案中,脲不加入或者不存在于该粘合剂中。
脲不能用于本发明中,因为大豆粉将不变性,并且脲酶将保留。Wescott也在US专利申请系列号12/869848和12/507247中揭示了脲酶必须变性(酶活性被杀死)来使得脲是可行的稀释剂。在本申请中,我们使用脲酶活性的大豆粉。
本发明的一方面提供了一种制造稳定的粘合剂的方法,该方法包含步骤:提供大豆粉的含水混合物,加入非脲稀释剂和将pH降低到小于5.0,优选小于4.5。
在另外一种实施方案中,非脲稀释剂是在大豆粉之前加入到水中的。
绝对必需的是降低本发明大豆粉的pH。用于处理大豆粉的酸可以是Bronsted或者路易斯酸类。使用通常的无机酸如硫酸或盐酸是优选的。
大豆粉中稀释剂的加入量取决于粘合剂的需要。例如,稀释剂含量可以调整以控制最终粘合剂的流动特性或者玻璃化转变温度(Tg)。如果期望的话,这允许本发明的粘合剂喷雾干燥和转化成可用的粉末粘合剂树脂。
在一种实施方案中,大豆粉中稀释剂的加入量可以是大约5份比1份大豆粉(固体/固体)到大约0.1份比1份大豆粉(固体/固体);最优选2份比1份大豆粉到大约0.5份比1份大豆粉。在稀释剂加入之前、之中或之后,该大豆粉可以加入到含水体系中。
本发明的粘合剂可以与任何乳液聚合物例如诸如聚醋酸乙烯酯(PVAc)乳液混合,来产生稳定的粘合剂。该乳液聚合物的加入水平是0.1-80%干固体重量,基于总粘合剂的干固体重量。
典型的,将未改性的大豆粉或者NaOH改性的大豆粉直接加入到乳化的聚合物中产生了具有差的稳定性和相容性的树脂。相反,将本发明的稳定的稀释剂-大豆粘合剂加入到乳液或者分散的聚合物中产生了稳定的、高度相容性粘合剂分散体,其可用于许多工业应用中。此外,所述组合是通过简单混合技术,使用本领域技术人员已知的在线混合、商业混合槽、薄槽或者反应器来完成的。混合温度不被认为是关键的,并且典型的使用室温,虽然令人期望的和可接受的是将本发明的稳定的大豆-稀释剂粘合剂与乳液或者分散的聚合物在较高的温度组合,这取决于用户的需要。可能需要用酸或者碱调整最终的pH来确保总体系最佳的稳定性。但是,这些调整典型地是相当温和的,并且是本领域技术人员已知的。例如,乳液或者分散体稳定性所必需的较小的调整会是期望的。
本发明的稳定的大豆-稀释剂粘合剂可以用作或者可以进一步通过加入合适的交联剂来改进。交联剂典型地加入到粘合剂中来提供另外的性能值,其操控了粘合剂现有的性能,例如耐水性,溶解性,粘度,存储寿命,弹性体性能,耐生物性,强度等。交联剂的作用(不管类型)是混入来提高粘合剂本身中的交联密度。这最好是用交联剂来实现的,其在每个分子中具有若干个反应性位置。
本发明所用的交联剂的类型和量取决于所期望的最终性能。另外,所用交联剂的类型和量可以取决于粘合剂中所用大豆粉的特性。
现有技术已知的任何蛋白质交联剂可以用于本发明的方法中。例如,该交联剂可以包含甲醛或者可以不包含甲醛。虽然无甲醛的交联剂是在许多内部应用中是非常令人期望的,但是对于一些外部应用来说,含甲醛的交联剂仍然是可接受的。
与本发明的粘合剂一起使用的可能的无甲醛的交联剂包括异氰酸酯如聚合的亚甲基二苯基二异氰酸酯(polymeric methylene diphenyl diisocyanate,pMDI)和聚合的六亚甲基二异氰酸酯(pHMDI),胺-表氯醇加成物,环氧,醛和脲-醛树脂,其能够与大豆粉反应。当无甲醛的交联剂用于本发明中时,它的量是0.1-80%,基于总干燥粘合剂的干重。优选的无甲醛交联剂是聚合的亚甲基二苯基二异氰酸酯(pMDI),并且用量是总干重的0.1-80%。
胺-表氯醇树脂是另一类可能的无甲醛的交联剂。它们定义为通过表氯醇与胺官能化合物反应所制备的那些。在它们中是聚酰胺胺-表氯醇树脂(PAE树脂),聚亚烷基聚胺-表氯醇(PAPAE树脂)和胺聚合物-表氯醇树脂(APE树脂)。PAE树脂包括基于仲胺的氮杂环丁烷鎓(azetidinium)官能化PAE树脂例如KymeneTM557H,KymeneTM557LX,KymeneTM617,KymeneTM624和Hercules CA1000,全部获自Hercules Incorporated,Wilmington DE,叔胺聚酰胺系环氧化物官能化树脂和叔胺聚酰胺亚脲系环氧化物官能化PAE树脂例如KymeneTM450,获自HerculesIncorporated,Wilmington DE。一种合适的交联PAPAE树脂是KymeneTM736,获自Hercules Incorporated,Wilmington DE。KymeneTM2064是一种APE树脂,其也获自Hercules Incorporated,Wilmington DE。它们是广泛使用的市售材料。它们的化学性质描述在下面的参考文献中:H.H.Espy,“Alkaline-Curing Polymeric Amine-Epichlorohydrin Resins”,在Wet Strength Resins and Their Application,L.L.Chan,Ed.,TAPPI Press,Atlanta GA,第13-44页(1994)。还可以使用低分子量胺-表氯醇缩合物作为无甲醛交联剂,如Coscia(US专利No.3494775)所述。
PAE树脂是典型的碱固化体系。因此在本发明中,大豆-稀释剂和PAE的组合会产生均匀的混合物,其在若干个月内是粘度和性能都稳定的。这是相对于以前的大豆-PAE体系(其需要在即将使用前混合)的一个明显改进。
可能的含甲醛的交联剂包括甲醛,酚甲醛,脲甲醛,三聚氰胺脲甲醛,三聚氰胺甲醛,酚间苯二酚甲醛及其任意组合。当含甲醛的交联剂用于本发明时,它们的用量是总粘合剂组合物干重的1-80%。在本发明的一种实施方案中,该交联剂包含酚甲醛的量是总干重的1-80%。
不管所用的具体交联剂,该交联剂典型地是在即将使用之前加入到大豆-稀释剂粘合剂中的(例如在制造木质纤维素复合材料中),但是在某些情况中可以在使用前数天或者甚至数周加入。
优选的非脲稀释剂包括多元醇如甘油,乙二醇,丙二醇,新戊二醇,其聚合物形式(例如聚乙二醇-PEG),或者任何其他可利用的含羟基的单体或者聚合物材料。甘油是最优选的,并且任何级别都是可接受的。加入豆油或者任何其他可水分散的脂肪酸或者甘油三酸酯也是可接受的,只要能够实现均匀混合物就行。其他另外的稀释剂(其仅仅用于填充该固体)也是可接受的,例如面粉,滑石,粘土等。
该非脲稀释剂的混入水平可以是总粘合剂的0.1重量%向上到70重量%,基于固体干重。它们可以在所述方法的任何步骤过程中混入,包括大豆粉加入之前、之中或者之后。
本领域通常使用的加工或性能改性剂例如消泡剂、润湿剂等也可以加入到最终的粘合剂中。
也可以使用传统的大豆蛋白质改性剂;例如加入亚硫酸氢钠来通过降低二硫化物键来降低粘度。
本发明的大豆/稀释剂粘合剂的最终pH可以用任何合适的Bronsted或者路易斯酸或碱来调整。本发明的粘合剂的最终pH小于5,优选小于4.5和大于2.0,优选大于3.0。本领域技术人员将明白如何均操控粘合剂的pH(在下面的实施例中描述)和应用需要具有多高或多低pH的粘合剂。典型地,最终的pH将基于应用或所用的交联剂类型来选择。
本发明的方法还可以包括增加喷雾-或者冷冻-干燥步骤来产生粉末粘合剂。
本发明的稳定的大豆-稀释剂粘合剂可以用于许多工业应用中。例如该粘合剂可以以下面的量施用到合适的基底上:1-25%干重(1份干粘合剂/100份基底到25干粘合剂/100份基底),优选是1-10重量%和最优选2-8重量%。一些合适的基底的例子包括但不限于木质纤维素材料、浆或者玻璃纤维。粘合剂可以通过本领域已知的任何手段施用到基底上,包括辊涂,刮刀式涂布,挤出,幕涂,发泡涂布机和喷涂机例如旋转盘式树脂涂布机。
本领域技术人员将理解如何使用本发明的粘合剂/分散体,使用本领域已知的参考文献来制备木质纤维素复合材料。参见例如“Wood-basedComposite Products and Panel Products”,Wood Handbook–Wood as an Engineering Material,Gen.Tech.Rep.FPL-GTR-113的第10章,第463页,U.S.Department of Agriculture,Forest Service,Forest ProductsLaboratory,Madison,WI(1999)。许多材料可以使用本发明的粘合剂/分散体来制备,包括颗粒板,定向条板(OSB),晶片板,纤维板(包括中密度和高密度纤维板),平行的条木(PSL),层合的条木(LSL),定向的条木(OSL)和其他类似产品。木质纤维素材料例如木头,木浆,禾草(包括水稻,小麦或大麦),亚麻,大麻和甘蔗渣可以用于制造本发明的热固性产品。木质纤维素产品典型地是通过将粘合剂与粉末、粒子、纤维、碎片、薄片纤维、晶片、装饰件、刨花、锯末、禾草、茎秆或亚麻皮形式的基底混合,然后压缩和加热所形成的组合物,来获得固化的材料。在与本发明的粘合剂混合之前,该木质纤维素材料的含湿量应当是2-20%。
本发明的粘合剂也可以用于生产胶合板(plywood)或层合的单板木材(veneer lumber,LVL)。例如在一种实施方案中,该粘合剂可以通过辊涂、刮刀式涂布、幕涂或者喷涂施用到单板表面上。多个单板然后叠置来形成所需厚度的片。该垫子或者片然后置于通常加热的压机(例如压盘)中,并且压缩来进行材料形成板的合并和固化。纤维板可以通过湿粘结/湿压方法、干粘结/干压方法或者湿粘结/干压方法来制造。
除了木质纤维素基底之外,本发明的粘合剂可以与基底例如塑料、玻璃绒、玻璃纤维、其他无机材料及其组合一起使用。
下面的实施例当然提供来仅仅用于说明性的目的,并非打算对本发明的范围进行任何的限制。确实的,除了这里所示和所述的那些之外,从前述说明和下面的实施例,本发明不同的改变将对本领域技术人员而言变得显而易见,并且落入附加的权利要求书的范围。
实施例和评价方法。
评估了粘合剂下面的特性:
1)物理性能-Brookfield粘度(在全部的情况中,RV10RPM),并且转筒的选择取决于产品的粘度,pH和室温稳定性(粘度和通过大豆腐烂或者类似于牛奶的变质明显的开始所确定的生物变化)。为了降低经常由于大豆粘合剂触变性引起的临时性粘度升高的影响,在任何粘度测量之前将该粘合剂快速搅拌30秒。
2)粘合剂结合强度-通过下面的ABES和颗粒板程序来测量:
ABES程序。
样品制备:木材样品是使用自动结合评价系统(ABES)冲压设备从枫木单板上冲压出来的,这样最终的尺寸沿着颗粒是11.7cm,垂直于颗粒是2.0cm和0.08cm厚。将待测试的粘合剂施用到样品的一端上,以覆盖整个的交叠面积,其通常是3.8-4.2mg/cm2,基于湿态。该样品然后结合到第二单板(开放时间小于15秒来确保优异的转移)和置于ABES单元中,以使得该结合样品的交叠区域是1.0cm×2.0cm。除非另有指示,否则将全部样品在120℃用9.1kg/cm2的压力压制2.0分钟。然后将全部结合的样品在22℃和50%相对湿度的受控环境中调整至少48小时。
强度测试:对于每个树脂,以上述方式制备了10个样品。在调整后,10个样品中的5个是使用ABES仪器在干燥条件中测试的。记录了样品破裂时的最大负荷。将它们称作干燥强度样品。将其余5个样品置于22℃的水浴中4小时。将该样品从水浴中移去,并且立即以上述方式测试。将这些样品称作湿样品。对于每个树脂,所报告的值是5个样品的平均值。所报告的误差是标准偏差。对于干评估和湿评估二者来说,这种方法典型的偏差系数(COV)是大约15%;按照木材本身中的可变性,这被认为是优异的。
颗粒板资格-样品是使用下面所述的“颗粒板程序”来制备的,然后评估内结合(IB),断裂模量(MOR)和弹性模量(MOE)。
用于12”X12”Carver水电压机的颗粒板程序
这些面板的目标密度和厚度是46lb/ft3,厚度是1/2”。在整个面板中使用市售的面装饰。装饰是1.5-4.0%MC。压机温度是170℃。
颗粒板程序:将面装饰(face furnish)称重到被认可的容器中,并且置于混合碗中。称重树脂来将要干装饰的7.0%固体树脂(最接近0.0g)用于连接到空气雾化喷嘴上的注射器中,并且施用于装饰。使用混合器混合1分钟来彻底混合该树脂化粒子。将剥离纸置于实验室均压板(caul plate)上,并且将10”X10”成型盒置于该剥离纸顶上。将该树脂化装饰以半平坦层置于成型盒中。通过人工将装饰沿着均压板铺开形成垫子。重要的是该层是尽可能平坦的铺展,来避免密度分布问题。将该板在冷压机上以100psi压60秒。将第二片剥离纸和均压板置于预压制的垫子的顶上。放入热压机中,并且关闭该压机到停1/2”和保持4min。从热压机上除去所述面板,并且冷却到室温。将该面板修剪到9”x9”和在测试之前,在80°F和30%相对湿度的环境受控室中调整全部测试样品至少48小时。
这些实施例的原材料如下:大豆粉:大豆粉-90(90PDI,200目),由Cargill(Decator,IL)提供;pMDI:RubunateTMFC3345,由HuntsmanInternational(Woodlands,TX)提供;PVAc:Duracet,由Franklin(Columbus,OH)提供;其他稀释剂:由Aldrich(Milwaukee,WI)提供。
实施例1:若干种大豆-稀释剂体系是使用多种稀释剂类型和量以及变化的总固体和最终pH来制备的。
标准制备程序:在圆底烧瓶中加入水和非脲稀释剂。然后将亚硫酸氢钠以1%的浓度加入到干大豆粉中。然后在1-5分钟内加入大豆粉,并且同时快速搅拌。将该混合物搅拌15-30分钟。然后通过逐滴加入50%硫酸,将pH调整到期望的终点。下表1表示了这些具体实施例的特性。
表1
实施例1的大豆-稀释剂产品的特性
备注:G=甘油,EG=乙二醇,PPG=丙二醇,PEG=聚乙二醇
表1的结果显示了在宽范围的稀释剂类型和浓度上,本发明生产高固体、低粘度粘合剂的通用性。
实施例2-与pMDI混合:
将实施例1所述的几种基础树脂与pMDI(RubunateTMFC3345)组合,来评估对于结合性能(通过ABES方法测量)和对于物理性能二者的影响。所选择的非脲稀释剂是甘油(G),乙二醇(EG)和PEG-8000MW(PEG)。在评估之前,在烧杯或者圆底烧瓶中简单混合5分钟来进行混合。全部的混合物是均匀和容易处理的。这些混合物的特征表示在表2中。
表2所述粘合剂的干强度和湿强度是使用ABES方法评估的。这些结果表示在表3和图1和2中。
表2与pMDI混合的大豆:稀释剂的特性
表3与pMDI混合的大豆:稀释剂的结合强度(ABES)
实施例 | 基础树脂 | 稀释剂类型 | pMDI(PPH)* | 干强度(N) | 湿强度(N) |
2-1 | 1-1 | G | 0 | 383 | 0 |
2-2 | G | 20 | 438 | 82 | |
2-3 | G | 50 | 613 | 170 | |
2-4 | 1-3 | EG | 0 | 261 | 0 |
2.5 | EG | 20 | 475 | 159 | |
2-6 | EG | 50 | 561 | 203 | |
2-7 | 1-6 | PEG | 0 | 592 | 42 |
2-8 | PEG | 20 | 776 | 73 | |
2-9 | PEG | 50 | 684 | 94 |
实施例2的讨论:将pMDI加入到大豆-稀释剂体系中产生了具有明显更高的干强度和湿强度的最终粘合剂。此外,这些粘合剂是均匀的,其由于pMDI材料的有机性而是相当令人惊讶和意外的,并且最终固含量和粘度值非常适于商业喷涂使用。
实施例3:混合有pMDI的大豆:稀释剂(S:G=1:1)(pH<5)的粘度和粘度稳定性
本发明的显著特点在于它不仅能够产生高固体和低粘度树脂,而且还能够产生表现出相对于现有技术的明显改进的粘度稳定性的粘合剂配制品。
将来自实施例1的树脂与pMDI以类似于实施例2所述的方式混合。在这个实施例中,起始树脂的pH小于5以表现出获得最终粘合剂的益处,该粘合剂的粘度是低的,并且表现出更好的粘度稳定性。这些结果与实施例4(pH>5)的结果一起表示在表4和图3中。
实施例4:(对比例)与pMDI混合的大豆:稀释剂(S:G=1:1)(pH>5)的粘度和粘度稳定性:
与实施例3相同,但是pH>5。
表4
与pMDI混合的大豆:稀释剂(1:1)的随pH变化而变化的初始粘度和粘度稳定性
实施例5:与pMDI混合的大豆:稀释剂(S:G=2:1)(pH<5)的粘度和粘度稳定性:
与实施例3相同,但是S:G=2.0
实施例6:与pMDI混合的大豆:稀释剂(S:G=2:1)(pH>5)的粘度和粘度稳定性:
与实施例5相同,但是pH>5。
表5
与pMDI混合的大豆:稀释剂(2:1)随pH变化而变化的初始粘度和粘度稳定性
图4图示了实施例5.4(低pH)和6-4(高pH)的50/50大豆/稀释剂的数据
实施例3-6的讨论:pH降低到小于5,明显导致了粘度稳定性的显著改进;这是从较低的初始粘度值以及粘度稳定性曲线下降的斜率二者观察到的。这种趋势在高交联浓度体系例如具有50%pMDI的体系中是最明显的。
实施例7:颗粒板面板
在与各种量的pMDI混合后,根据实施例2所述的程序,由实施例1-8所述的树脂制造了若干个实验室颗粒板面板。全部配方的最终pH小于5。该颗粒板制备程序在这个文献前面描述过。在这个实施例中评估了pMDI添加的若干个浓度。另外,实施例7-1和7-2是处于两个不同的负载浓度的100%的pMDI对照面板。这结果表示在表6中。
表6
由大豆:稀释剂-pMDI混合物制造的颗粒板
实施例7的讨论:基于大豆-稀释剂的粘合剂生产高强度颗粒板面板的能力已经得以证实。最明显地,大豆-稀释剂实施例(7-3和7-6)都是比相当负荷的pMDI对照面板(7-1)明显更高的强度面板。这证实了用明显降低用量的pMDI来生产优质pMDI面板的能力。
Claims (14)
1.一种稳定的粘合剂组合物,其包含在水中的非脲稀释剂和大豆粉,其中,pH小于5.0和其中该组合物中没有加入脲。
2.权利要求1的组合物,其进一步包含交联剂。
3.权利要求2的组合物,其中交联剂在所述组合物中的量是0.1-80%固体,基于总干重。
4.权利要求2的组合物,其中该交联剂包含选自下面的无甲醛交联剂:异氰酸酯、聚胺表氯醇树脂、聚酰胺胺-表氯醇树脂、聚亚烷基聚胺-表氯醇、胺聚合物-表氯醇树脂环氧、醛、醛淀粉、二醛淀粉、乙二醛、脲乙二醛、脲-醛树脂及它们的混合物。
5.权利要求2的组合物,其中该交联剂包含异氰酸酯。
6.权利要求2的组合物,其中该交联剂包含聚合的亚甲基二苯基二异氰酸酯。
7.权利要求2的组合物,其中该交联剂包含聚酰胺胺-表氯醇树脂。
8.权利要求2的组合物,其中该交联剂包含选自下面的含甲醛的交联剂:甲醛、酚甲醛、三聚氰胺甲醛、脲甲醛、三聚氰胺脲甲醛、酚间苯二酚甲醛及它们的任意组合。
9.前述任一项权利要求所要求的组合物,其进一步包含乳液聚合物的加入。
10.权利要求9的组合物,其中该乳液聚合物在组合物中的量是0.1-80%干重,基于总干重。
11.权利要求9或10的组合物,其中该乳液聚合物包含聚醋酸乙烯酯(PVAc)。
12.前述任一项权利要求的组合物,其进一步包含稀释剂。
13.权利要求12的组合物,其中该稀释剂选自甘油、乙二醇、丙二醇、新戊二醇、其聚合物形式及它们的任意组合。
14.权利要求12的组合物,其中该稀释剂是甘油。
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RU (1) | RU2606620C2 (zh) |
WO (1) | WO2012112734A1 (zh) |
ZA (1) | ZA201306946B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110799617A (zh) * | 2017-06-29 | 2020-02-14 | 生态合成股份有限公司 | 具有粘着性的粘合剂以及在木质复合制品中的用途 |
CN112063364A (zh) * | 2020-09-14 | 2020-12-11 | 郑州轻院产业技术研究院有限公司 | 一种植物蛋白基无甲醛胶粘剂 |
US11530343B2 (en) | 2014-12-23 | 2022-12-20 | Ecosynthetix Inc. | Biopolymer and isocyanate based binder and composite materials |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2016198705A1 (es) * | 2015-06-12 | 2016-12-15 | Grupo Garnica Plywood, S.A. | Tablero de contrachapado para la fabricación de mobiliario de caravanas y procedimiento de obtención de dicho tablero |
US20200071530A1 (en) * | 2018-08-30 | 2020-03-05 | Solenis Technologies, L.P. | Unitary mat having increased green strength and method of forming the same |
EP3999590A1 (en) | 2019-07-15 | 2022-05-25 | Agroils Technologies S.p.A. | Formaldehyde-free binders and methods for producing the same |
IT202000003022A1 (it) * | 2020-02-14 | 2021-08-14 | Agroils Tech S P A | Composti leganti a base biologica e metodi per produrli |
IT202100031619A1 (it) * | 2021-12-17 | 2023-06-17 | Pozzi Arosio S R L A Socio Unico | Materiale poliuretanico composito |
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WO2008011455A1 (en) * | 2006-07-18 | 2008-01-24 | Heartland Resource Technologies | Stable adhesives from urea-denatured soy flour |
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US7252735B2 (en) | 2002-05-13 | 2007-08-07 | State Of Oregon Acting By And Through The Oregon State Board Of Higher Education On Behalf Of Oregon State University | Formaldehyde-free lignocellulosic adhesives and composites made from the adhesives |
CA2458159A1 (en) * | 2004-01-22 | 2005-07-22 | The State Of Oregon Acting By And Through The State Board Of Higher Educ Ation On Behalf Of Oregon State University | Formaldehyde-free adhesives and lignocellulosic composites made from the adhesives |
ATE533823T1 (de) | 2004-04-06 | 2011-12-15 | Hercules Inc | Wasserbeständige klebemitteldispersionszusammensetzungen aus pflanzenprotein |
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2012
- 2012-02-16 CA CA2825527A patent/CA2825527C/en active Active
- 2012-02-16 US US13/397,829 patent/US20120214909A1/en not_active Abandoned
- 2012-02-16 CN CN201280009196XA patent/CN103403122A/zh active Pending
- 2012-02-16 EP EP12705764.4A patent/EP2675861A1/en not_active Withdrawn
- 2012-02-16 KR KR1020137024149A patent/KR101941717B1/ko active IP Right Grant
- 2012-02-16 BR BR112013020735A patent/BR112013020735A8/pt not_active Application Discontinuation
- 2012-02-16 AU AU2012217689A patent/AU2012217689B2/en not_active Ceased
- 2012-02-16 MX MX2013008858A patent/MX2013008858A/es unknown
- 2012-02-16 MY MYPI2013701306A patent/MY170457A/en unknown
- 2012-02-16 WO PCT/US2012/025348 patent/WO2012112734A1/en active Application Filing
- 2012-02-16 RU RU2013142176A patent/RU2606620C2/ru active
-
2013
- 2013-08-12 CL CL2013002339A patent/CL2013002339A1/es unknown
- 2013-09-16 ZA ZA2013/06946A patent/ZA201306946B/en unknown
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US20050166796A1 (en) * | 2003-12-31 | 2005-08-04 | Sun Xiuzhi S. | Adhesives from modified soy protein |
WO2008011455A1 (en) * | 2006-07-18 | 2008-01-24 | Heartland Resource Technologies | Stable adhesives from urea-denatured soy flour |
CN101511925A (zh) * | 2006-07-18 | 2009-08-19 | 哈特兰德资源技术公司 | 来自尿素变性大豆粉的稳定的粘合剂 |
CN101889064A (zh) * | 2007-10-09 | 2010-11-17 | 赫尔克里士公司 | 含有交联剂的粘合剂组合物 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US11530343B2 (en) | 2014-12-23 | 2022-12-20 | Ecosynthetix Inc. | Biopolymer and isocyanate based binder and composite materials |
CN110799617A (zh) * | 2017-06-29 | 2020-02-14 | 生态合成股份有限公司 | 具有粘着性的粘合剂以及在木质复合制品中的用途 |
CN112063364A (zh) * | 2020-09-14 | 2020-12-11 | 郑州轻院产业技术研究院有限公司 | 一种植物蛋白基无甲醛胶粘剂 |
Also Published As
Publication number | Publication date |
---|---|
ZA201306946B (en) | 2015-04-29 |
WO2012112734A1 (en) | 2012-08-23 |
CL2013002339A1 (es) | 2013-12-13 |
BR112013020735A8 (pt) | 2018-02-06 |
EP2675861A1 (en) | 2013-12-25 |
RU2013142176A (ru) | 2015-04-10 |
KR101941717B1 (ko) | 2019-01-23 |
CA2825527A1 (en) | 2012-08-23 |
MX2013008858A (es) | 2013-08-14 |
US20120214909A1 (en) | 2012-08-23 |
AU2012217689B2 (en) | 2015-08-27 |
RU2606620C2 (ru) | 2017-01-10 |
BR112013020735A2 (pt) | 2016-10-18 |
KR20140012665A (ko) | 2014-02-03 |
MY170457A (en) | 2019-08-02 |
CA2825527C (en) | 2016-04-26 |
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