CN101155646B - 分散体系 - Google Patents

分散体系 Download PDF

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CN101155646B
CN101155646B CN2006800113925A CN200680011392A CN101155646B CN 101155646 B CN101155646 B CN 101155646B CN 2006800113925 A CN2006800113925 A CN 2006800113925A CN 200680011392 A CN200680011392 A CN 200680011392A CN 101155646 B CN101155646 B CN 101155646B
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德奥古斯蒂努斯·尤金·赫克·凯吉则
利奥波德·弗拉其苏斯·韦南度斯·弗洛伊格尔斯
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Abstract

本发明涉及三聚氰胺粉末在液体中的分散体系，其中所述分散体系含有分散剂，所述分散剂包含苯乙烯-顺丁烯二酸酐共聚物。本发明还涉及用于制备所述分散剂的方法，并涉及其在胶粘剂组合物、涂料或层压材料中的用途。

Description

分散体系
本发明涉及分散体系，特别是三聚氰胺在液体中的分散体系。
在EP 1 099 726 A2中，公开了水性三聚氰胺树脂分散体系，所述分散体系包含由阳离子和阴离子保护性胶体的组合稳定的三聚氰胺树脂作为连续相。在EP 1 099 726 A2中，所述阳离子保护性胶体优选地包含阳离子淀粉，所述阴离子保护性胶体优选地包含丙烯酸、丙烯酸甲酯和2-丙烯酰胺基-2-甲基丙磺酸的共聚物。
已知分散体系的缺点在于保护性胶体体系相当复杂，因此需要大量努力来产生；因此，其也是昂贵的体系。
本发明的目的是减少所述缺点。通过三聚氰胺在液体中的分散体系达到了所述目的，其中所述分散体系含有分散剂，所述分散剂包含苯乙烯-顺丁烯二酸酐共聚物。
在本发明的范围内，术语“分散体系”是指包含两个相的体系，其中一项是连续相，另一相是不连续相，所述不连续相被分散在所述连续相中。因此术语“分散体系”比起气体在液体中的体系(泡沫)、液体在液体中的体系(乳液)和固体在液体中的体系(溶胶)更加宽泛，并包括后三种体系。根据本发明的分散体系中的不连续相以颗粒的形式存在。如本文所指，术语“颗粒”包括固体实体，也包括液体实体。尽管被分散的颗粒的尺寸可在广泛的界限内变化，但是优选重均尺寸位于0.1μm和100μm之间，更优选地在0.5μm和75μm之间、1μm和50μm之间、1.5μm和25μm之间、或甚至在1.75μm和15μm之间或在2μm和10μm或5μm之间。
如所已知的，分散体系通常含有特别地作用以帮助产生或稳定分散体系和/或影响颗粒尺寸的化合物或化合物的混合物。这类化合物在本发明上下文中称为分散剂。因此本文使用的术语“分散剂”比保护性胶体或表面活性剂更加宽泛，并包括后两者。分散剂的使用和存在有助于产生稳定的分散体系。在本发明上下文中，术语“稳定的”涉及分散体系时可具有两种含义：分散体系制备后至少30分钟(或甚至至少1小时，或优选地至少24小时)被分散的颗粒不分离出来、凝聚或沉降；或当被分散的颗粒分离出来、凝聚或沉降后可通过搅拌被容易地再分散。
根据本发明的分散体系是三聚氰胺在液体中的分散体系。在本发明的实施方式中，三聚氰胺以基本未反应的形式存在，并构成固体或液体形式的不连续相的一部分(例如10重量％(wt.％)或25wt.％)、大部分(例如55wt.％或75wt.％)或基本全部。这不排除三聚氰胺也被包括在作为连续相的液体中；当三聚氰胺在液相中具有一定溶解度时就是这样的情况。如所已知的，三聚氰胺可稍微溶解在某些液体如水或氨水中。在本发明上下文中，术语“基本上构成所有”、“基本上由......构成”和等效术语具有下述含义：对本发明的功能、效果或目的有影响的其他化合物或手段不存在或不被采用。
可存在于分散体系的基本未反应形式的固体三聚氰胺的量在本文被称为粉末含量，可在广泛的界限之间变化。在某些情况下，理想的是，粉末含量尽可能的高，例如当预期到分散体系的运输时。本发明的一个优点在于所述分散体系的粉末含量可以非常高，而同时分散体系保持期望的特性，如稳定性、被分散相的不连续性和将分散体系稀释为具有更低粉末含量的稳定、均一分散体系的能力。我们发现根据本发明的分散体系的粉末含量可高达60wt.％、65wt.％、70wt.％或甚至75wt.％到80wt.％。因此，分散体系中三聚氰胺的量优选为1wt.％和80wt.％之间，更优选地5wt.％和75wt.％之间。
根据本发明的分散体系包含液体作为连续相。可能必须建立与室温和大气压不同的温度和压强条件，以确保应当是液相的化合物的确是液体形式；这是使用例如氨水时的情况。可在根据本发明的分散体系中用作连续相的液体实例为：水，氨水，醇例如甲醇、乙醇、丙醇和丁醇，非质子极性溶剂如二甲基亚砜(DMSO)和二甲基甲酰胺(DMF)。可在根据本发明的分散体系中用作连续相的液体的其他实例是多元醇；具体地，三聚氰胺在多元醇中的分散体系由于阻燃特性被有利地使用，所述阻燃特性由例如聚氨基甲酸酯体系(如泡沫)的典型终产物中的三聚氰胺粉末得到，所述典型终产物由多元醇作为化学构造链段制成。多元醇在本文中应理解为含有大量羟基的低分子量水溶性聚合物和低聚物。特定的实例包括聚醚型多元醇(例如Voranol 3136，供应商Dow Plastics，或Caradol SP50-01，供应商Shell Chemicals或Alcupol F-5611，供应商Repsol)。
水性体系被优选作为根据本发明的分散体系中的液体。在本发明一个特别优选的实施方式中，液体为包含氨基塑料的水性体系；达到这样的一个方式是确保：包含在连续相中的氨基塑料树脂未反应达到其不再可溶的程度。
根据本发明的分散体系含有分散剂，所述分散剂包含苯乙烯-顺丁烯二酸酐共聚物。苯乙烯-顺丁烯二酸酐共聚物本身是已知的。如所已知的，所述共聚物可例如用碱(例如NaOH或KOH)处理，从而在共聚物中产生离子基。这样的优点在于在多种液体(例如水性体系)中共聚物成为可溶性的或更加可溶。在本发明上下文中，术语“苯乙烯-顺丁烯二酸酐共聚物”是指共聚物本身和/或指其被处理从而产生离子基之后的共聚物。
优选的是，苯乙烯-顺丁烯二酸酐共聚物的重均分子量(Mw)大于1,000、1,500、3,000、10,000、50,000或甚至100,000。我们发现根据本发明的分散体系中，苯乙烯-顺丁烯二酸酐共聚物的分散能力和所形成的分散体系的稳定性随着苯乙烯-顺丁烯二酸酐共聚物的Mw增长而增长。优选地，所述分子量Mw至多为3,000,000或2,000,000，更优选至多为1,000,000。
根据本发明的共聚物中苯乙烯与顺丁烯二酸酐的摩尔比在广泛的界限之间变化，优选地在1∶0.1和1∶1之间，更优选在1∶0.5和1∶1之间。
如所已知的，单体苯乙烯和顺丁烯二酸酐单元可以以基本上无规的形式，或以嵌段共聚物的形式，或以交替(alternation)，或以上述的任何组合存在于共聚物中。根据本发明，这些可能中的任何一种是合适的，但是当苯乙烯与顺丁烯二酸酐的摩尔比基本上是1∶1时，优选交替共聚物，当苯乙烯与顺丁烯二酸酐的摩尔比低于1∶1(例如1∶0.5)时，优选无规和部分交替共聚物。
如所已知的，苯乙烯顺丁烯二酸酐共聚物的水性溶液可通过在提高的温度下在水中用碱处理所述共聚物来制备。合适的苯乙烯顺丁烯二酸酐共聚物的实例为
Figure GSB00000152287200041
(供应商：Hercules；分子量约350,000；苯乙烯与顺丁烯二酸酐的比例1∶1)。
包含在根据本发明的分散体系中的分散剂包含苯乙烯顺丁烯二酸酐共聚物。分散剂可以包含其他化合物，例如其他类型的分散剂；然而优选的是，根据本发明的分散体系中的分散剂包含至少50wt.％、60wt.％或甚至至少75wt.％或80wt.％的苯乙烯顺丁烯二酸酐共聚物，更优选地，分散剂基本上由苯乙烯顺丁烯二酸酐共聚物组成。
被添加的分散剂的量可在广泛的界限内变化，这取决于分散剂的确切性质、构成连续相的液体，还取决于要达到的期望颗粒尺寸等。优选地，根据本发明的分散体系含有0.01wt.％和10wt.％之间的分散剂，更优选地在0.05wt.％和7.5wt.％之间、0.2wt.％和5wt.％之间或1wt.％和3wt.％之间。
根据本发明的分散体系的pH可在广泛的界限内变化，优选在3和11之间或4和10之间，同时仍然维持稳定。如果存在三聚氰胺，则其典型地具有缓冲性质，并会趋向于将分散体系的pH通常影响至5到8或9的范围内。
使用根据本发明的分散体系的另一优点在于所述分散体系可具有高固体含量。分散体系的固体含量在本文中定义为不是作为分散体系中的连续相的液体的和(当颗粒包含氨基塑料树脂的情况下)不是作为制备氨基塑料树脂中的连续相的液体的所有化合物总和的重量百分比。所述两种液体可以是同一液体，例如当分散体系的最终形式在树脂制备中形成时；所述两种液体可以是相同或不同的，例如当分散体系通过添加经制备的氨基塑料树脂或分散至作为分散体系连续相的液相中而产生时。根据本发明的分散体系的固体含量可在广泛的界限之间变化，这取决于分散体系的进一步用途等。优选地。固体含量为至少5％、10％、15％、20％或甚至25％或30％。优选地，固体含量为至多70％、65％、60％、55％、50％或甚至45％。
本发明还涉及用于制备分散体系的方法，所述方法包括将液体第一相和第二相合并的步骤，其中在将两相合并由此形成所述分散体系之前、之中或之后添加包含苯乙烯-顺丁烯二酸酐共聚物的分散剂，其中所述液体第一相是连续相，其中第二相含有三聚氰胺粉末。
两相的合并可通过简单地将其混合来完成。这样的一个实例是将三聚氰胺粉末加入水中。
可合并两相的另一方式是通过原位产生它们。
在根据本发明的方法中，向体系中添加分散剂，这可在两相合并完成之前、之中或之后进行。优选地，在将两相合并之前或之中向将会作为连续相的液体中添加分散剂。
制备分散体系时，pH可在广泛的界限内变化；上文对于所获得的分散体系所给出的范围也适用于其制备。
本发明还涉及根据本发明的分散体系在制备胶粘剂组合物、涂料或层压材料中的用途。这可由根据本发明的分散体系完成，或通过将根据本发明的分散体系与其他成分(例如非分散剂氨基塑料树脂)组合而完成。如技术人员所已知的，如典型指出的用途包含将分散体系与催化剂或可能的其他添加剂的最终组合。
如所已知的，术语“氨基塑料树脂”是指氨基化合物与醛的反应产物。氨基化合物的实例为尿素和三聚氰胺，醛的实例为甲醛和烷醇半缩醛，例如根据在WO 03/101973中第2页第21行到第3页第15行中公开的式(II)的化合物。
氨基塑料树脂如三聚氰胺-甲醛树脂、脲-甲醛树脂或三聚氰胺-脲-甲醛树脂的制备本身是已知的。可参考例如W.Becker，D.Braun的″KunststoffHandbuch，10-Duroplaste″，1988Carl Hanser Verlag；更具体地参考第41页及以后的″Melaminharze″一章。
本发明借助以下实施例被进一步说明，而不受其限制。下面的实施例1和实施例2分别示出了如何将分散体系用于制备经涂覆的基材或“低压层压板”(即LPL)；但是实施例1和实施例2中的分散体系本身并非本发明的一部分，而只是示出本发明的分散体系的可能用途。
实施例1
制备三聚氰胺-甲醛树脂分散体系
制备分散剂：制备苯乙烯顺丁烯二酸酐共聚物(
Figure GSB00000152287200061
供应商：Hercules)的水性溶液。将61克Scripset 520缓慢地加入455克被搅拌的水中。在得到合适的不含团块的浆料后，添加50克的25(wt.％)NaOH水溶液。发生到约40℃的放热反应。然后将该物料在搅拌下加热至82℃并保持45分钟。调节pH(只许增大)至6.5。
合成三聚氰胺-甲醛(MF)分散体系：将加入199克水的406克38.5wt.％甲醛水性溶液的pH用2M NaOH调节至9.0。加入394克三聚氰胺；然后将混合物加热回流。在三聚氰胺溶解并获得澄清溶液后，将混合物冷却至82℃。然后加入如上所述制备的145克分散剂溶液，并用HNO3将混合物的pH调节至7，而同时所述溶液被剧烈地搅拌。15分钟后观察到溶液清晰的转变点，即变白。溶液从乳白色转变为澄清的白色混浊分散体系。分散体系的缩合反应在转变点之后持续额外的9分钟，然后冷却至20℃。开始冷却后一分钟用5M NaOH将分散体系的pH调节至8.6。约需8克。在搅拌的同时将溶液冷却至20℃并储存在塑料瓶中。得到的分散体系具有55％的固体含量和1.65的甲醛比三聚氰胺的摩尔比。所述分散体系稳定数天。
制备经涂覆的基材
借助于小的刮刀辊将经合成的树脂分散体系涂布在山毛榉木(beechveneer)上。涂布湿的分散体系后，涂层看起来是白色的。在室温下干燥后，涂层成为白色表面。该干燥的经涂覆的基材在压机中30bar下在150℃被压制3分钟。压制后获得具有澄清透明涂层的基材。
实施例2
通过将具有1.7的甲醛比三聚氰胺摩尔比的澄清单相液体三聚氰胺-甲醛树脂与如实施例1中制备的三聚氰胺-甲醛分散体系组合来制备分散体系。由此制备的分散体系固体含量为58％，其中55％来自单相液体三聚氰胺-甲醛树脂，3％来自如实施例1制备的三聚氰胺-甲醛分散体系。另外，向分散体系中添加0.2wt％的湿润剂Netzmittel PAT959/9和0.2wt.％的脱模剂(release agent)PAT-2523。
将
Figure GSB00000152287200071
Décor纸(80g/m2)形式的20cmx20cm载体片用所制备的分散体系浸渍一次，然后在100℃下干燥420秒。然后将浸渍的纸载体在100kN和190℃下在MDF板上层压50秒。如技术人员所已知的，这些条件是用于制备所述的LPL(即“低压”层压板)的典型条件。令人惊奇的是，在20°测量的所获得的层压板的光泽度为120，与HPL(高压层压板)大致相同。如技术人员所知，用一次浸渍的载体制造的已知的LPL具有低于HPL的光泽度，在20°测量时典型地为95-100。
实施例3
制备具有高粉末含量的分散体系
利用水性KOH使得苯乙烯顺丁烯二酸酐共聚物(SMA 1000TM，供应商EIf Ato Fina)在水性体系中可溶。然后，将1份SMA 1000与75份三聚氰胺粉末(供应商：DSM；该三聚氰胺根据Stamicarbon气相方法制备)和24份水组合。搅拌后获得稳定的分散体系。所述分散体系呈糊状，但是当分散体系受到更高的剪切速率时其粘度下降。制备后一周，所述分散体系未显示相分离或沉积的迹象，从而证实其稳定性。分散体系可用水稀释至少于40％粉末含量而不具有形成团块的迹象。
实施例4
制备具有高粉末含量的分散体系
利用水性KOH使得苯乙烯顺丁烯二酸酐共聚物(SMA 1000TM，供应商EIf Ato Fina)在水性体系中可溶。然后，将1份SMA 1000与65份多晶三聚氰胺粉末(供应商：DSM；该三聚氰胺根据高压液相方法制备，是WO 99/46251范围内的产物)和34份水组合。搅拌后获得稳定的分散体系。所述分散体系呈糊状，但是当分散体系受到更高的剪切速率时其粘度下降。制备后一周，所述分散体系未显示相分离或沉积的迹象，从而证实其稳定性。分散体系可用热水稀释至少于40％粉末含量而没有形成团块的迹象。

Claims (7)

1.三聚氰胺粉末在液体中的分散体系，其中所述分散体系含有分散剂，所述分散剂含有苯乙烯-顺丁烯二酸酐共聚物。
2.如权利要求1所述的分散体系，其中所述苯乙烯-顺丁烯二酸酐共聚物已经过处理，从而使其能够溶于水性体系。
3.如权利要求1或2所述的分散体系，其中所述苯乙烯-顺丁烯二酸酐共聚物的重均分子量为1,000和1,000,000之间，其中所述苯乙烯-顺丁烯二酸酐共聚物中苯乙烯与顺丁烯二酸酐的摩尔比为1∶0.5和1∶1之间。
4.如权利要求1-2中任一项所述的分散体系，其中所述分散体系中的三聚氰胺的量为1重量％和80重量％之间。
5.如权利要求4所述的分散体系，其中所述液体含有水或多元醇。
6.用于制备如权利要求1-5中任一项所述的分散体系的方法，所述方法包括将液体第一相和第二相合并的步骤，其中在将两相合并由此形成所述分散体系之前、之中或之后添加包含苯乙烯-顺丁烯二酸酐共聚物的分散剂，其中所述液体第一相是连续相，其中所述第二相包含三聚氰胺粉末。
7.如权利要求1-5中任一项所述的分散体系在胶粘剂组合物、涂料或层压材料中的用途。
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