CN108350218B - 在反应性稀释剂中预浓缩和预活化的脂肪二酰胺添加剂组合物 - Google Patents

在反应性稀释剂中预浓缩和预活化的脂肪二酰胺添加剂组合物 Download PDF

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CN108350218B
CN108350218B CN201680062277.4A CN201680062277A CN108350218B CN 108350218 B CN108350218 B CN 108350218B CN 201680062277 A CN201680062277 A CN 201680062277A CN 108350218 B CN108350218 B CN 108350218B
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CN108350218A (zh
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M.Y.伯纳德
C.富利亚特
V.勒罗伊
T.索拉
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Arkema France SA
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Abstract

本发明涉及基于脂肪酸二酰胺的流变添加剂组合物,其为脂肪酸二酰胺已经预活化和预浓缩的并且包括:a)5重量%‑30重量%的基于12‑羟基硬脂酸和线型的、特别地为C5、C6或C7的脂族二胺的至少一种脂肪酸二酰胺,b)70重量%‑95重量%的包含一个脂环族基团或多个脂环族基团的至少一种单官能的(甲基)丙烯酸类反应性稀释剂,所述%相对于a)+b)计。本发明还涉及用于制备所述组合物的方法以及其作为在反应性粘合剂组合物例如涂料、模塑、复合材料、锚栓、密封剂组合物或用于立体光刻或用于3‑D喷墨打印制品的可光致交联组合物中的流变添加剂的用途。

Description

在反应性稀释剂中预浓缩和预活化的脂肪二酰胺添加剂组 合物
本发明涉及一种新颖的特定流变添加剂,其为基于已经预活化的脂肪酸二酰胺的组合物,特别地为凝胶或糊料(paste)形式,所述流变添加剂的脂肪酸二酰胺是预浓缩的并且所述流变添加剂包括基于12-羟基硬脂酸(12-HSA)和线型脂族二胺的微粒化的脂肪酸二酰胺和单官能的(甲基)丙烯酸类反应性稀释剂。本发明还涉及制备方法、包含所述特定添加剂的反应性-粘合剂组合物以及其在反应性粘合剂的反应性组合物中用于即时使用且不需要将所述脂肪二酰胺添加剂再活化的用途。因此,该特定添加剂的用途具体地以如下为目标:反应性粘合剂的反应性组合物,例如涂料组合物如油漆、清漆、表层凝胶(凝胶涂料,gel coat)或油墨,或乳香胶(mastic)、胶、胶粘剂或模塑组合物,复合材料组合物、化学锚栓组合物、密封剂组合物或者用于立体光刻或用于3D打印制品的可光致交联组合物,特别地通过喷墨来3D打印制品的可光致交联组合物。
流变添加剂例如脂肪酸二酰胺的活化包括,在将所述二酰胺在适用于二酰胺和最终用途或应用的稀释剂或增塑剂中以微粒化的粉末形式均匀分散之后,将所述分散体在取决于所述二酰胺和所述稀释剂的给定温度下的等温条件下维持足够的时间段直至其粘度增加和稳定并且获得物理凝胶。
由此活化的凝胶(也称为活化糊料)可首先通过使用引入到待试验(测试)的凝胶或糊料中且保持直立而不移动的木质刮铲的相当简易的试验来表征,条件是所试验的产物通过保持单相的所述流变凝胶或糊料充分活化,并且始终不使反应性稀释剂渗出。
更具体地,所述活化凝胶或糊料可根据标准ASTM D 217用针入度计(penetrometer)通过针入深度、或通过测量获得的凝胶的动态弹性模量而表征。活化凝胶的在根据标准ASTM D 217的针入度方面的典型值小于15mm或为至少104Pa的在23℃且以1Hz的动态弹性模量E’。
在惰性溶剂例如二甲苯中、任选地在溶剂与醇的混合物中或在乙酸乙烯酯中或在白色溶剂油(white spirit)中预活化的流变添加剂的商业糊料已经存在。然而,这些惰性溶剂是易燃的,伴随有蒸气(称为VOC的挥发性有机化合物)排放到大气中。这样的预活化添加剂的使用除了这些易燃的VOC排放的影响之外,作为反应性粘合剂的反应性组合物中的额外影响,还将具有由于所获得的最终制品或涂层的塑化效应而引起的对最终机械性能水平的负面影响。
EP 1 935 934记载了脂肪酸二酰胺添加剂在液体增塑剂中的预活化且预浓缩的组合物。该体系具有与以上已经提到的关于对用基于反应性粘合剂的反应性组合物获得的涂层或制品的机械性能水平的负面的塑化的缺点相同的缺点。此外,存在着增塑剂与反应性粘合剂组合物的反应性组分的相容性的问题。由于所述增塑剂是惰性的且不能与所述反应体系相容,所以它具有至少部分地迁移到所获得的涂层或制品的表面的趋势,产生了在所获得的最终制品或涂层的表面处的粘附的问题。
用基于单组分或双组分反应性粘合剂的反应性组合物所遇到的另外问题在于如下事实:在脂肪酸二酰胺添加剂活化期间,必须避免所述反应性组分在所述二酰胺在最终配制剂中原位活化期间、在聚合且特别是交联反应之前过早反应的风险。
为了克服所有这些缺点,本发明提出使用预活化组合物形式的流变添加剂,其脂肪酸二酰胺为预浓缩的,并且使用参与所述反应性组合物的反应的反应性稀释剂作为稀释剂,所述稀释剂为单官能的(甲基)丙烯酸酯单体。结果,所述稀释剂被化学整合(结合,integrate)到最终产物中并且不会使最终产物塑化,它也无法迁移到所获得的最终制品或涂层的表面,这(本发明)尽管使用了少量所述的预浓缩且已经预活化的添加剂,但是不需要使所述添加剂在包含反应性粘合剂的反应性组分的反应性组合物中活化,且因此避免了所述最终反应性组合物过早聚合、特别是交联的任何风险。因此,反应性粘合剂或最终应用配制剂的所述反应性组合物通过简单地稀释所述预活化、预浓缩的添加剂可具有期望程度的触变性并且可即时使用(进行反应)而不需要预先的适当长的原位活化步骤且因此没有任何过早反应的风险。
该方案的另一个优势在于如下可能性:在经由自由基途径的反应性体系中(不管是在辐射下或通过加热或者通过基于过氧化物或氢过氧化物的引发体系(进行))或通过与其中所述稀释剂为单丙烯酸酯的反应性氨基组分经由迈克尔加成(Michael addition)反应的反应,例如在环氧胺双组分反应性粘合剂的情形中,使用该预活化且预浓缩的添加剂,特别地为预活化的凝胶或糊料的形式。
本发明首先涉及脂肪酸二酰胺在所述反应性稀释剂中的预活化和预浓缩的组合物,该组合物可为预活化的糊料或凝胶的形式。
另一个主题涉及用于制备所述添加剂的方法。
本发明还涉及包含所述添加剂作为流变添加剂、特别地作为触变添加剂的反应性粘合剂的反应性组合物或配制剂。
最后,本发明涉及如根据本发明所限定的所述添加剂作为反应性粘合剂组合物的流变添加剂用于即时使用且不需要另外使所述添加剂原位活化的用途。
因此,本发明的第一主题为基于脂肪酸二酰胺的流变添加剂组合物,其脂肪酸二酰胺为已经预活化和预浓缩的并且该组合物包括:
a)5重量%-30重量%的基于12-羟基硬脂酸和线型脂族二胺(其特别地为C5、C6或C7的)的至少一种脂肪酸二酰胺,
b)70重量%-95重量%的包含(一个)脂环族基团或多个脂环族基团的至少一种单官能的(甲基)丙烯酸类反应性稀释剂,所述脂环族基团可被至少一个C1-C4烷基所取代,
所述%相对于a)+b)计。
在所述反应性稀释剂b)的情形中,所述脂环族基团为环状基团,其中所述环只由碳原子形成。
基于12-羟基硬脂酸和线型脂族二胺的脂肪酸二酰胺意指,其通过12-HAS和所述二胺的缩合获得。因为市售12-HAS的纯度可在85%-100%变化,所以(如果其不是以100%)如下是可能的:即除了12-HAS之外,还存在其它残留的C18脂肪酸、特别地占大多数(大于85%的残留的C18酸)的硬脂酸。
优选地,在根据本发明的添加剂组合物中,所述二胺为C6线型脂族二胺。更特别地,所述二胺为1,6-六亚甲基二胺。
所述二酰胺在固体二酰胺的合成和回收之后通过机械研磨或通过空气喷射来微粒化以优选地获得小于15μm、更优选地小于10μm的体均尺寸。所述尺寸可通过激光衍射测定。更特别地,相对于a)+b)计,所述二胺a)以在10%-25%范围内的重量含量存在,且所述稀释剂b)以在75%-90%范围内的重量含量存在。
单官能的(甲基)丙烯酸类单体反应性稀释剂b)优选地选自:二环戊二烯基(甲基)丙烯酸酯、降冰片基(甲基)丙烯酸酯、异冰片基(甲基)丙烯酸酯(IBO(M)A)、叔丁基环己醇(甲基)丙烯酸酯(TBCH(M)A)、三环癸烷二醇单(甲基)丙烯酸酯或3,3,5-三甲基环己醇(甲基)丙烯酸酯(TMCH(M)A)。
根据一个具体选项,所述单官能的(甲基)丙烯酸类单体反应性稀释剂b)为单丙烯酸酯。相应类型的添加剂特别地适合作为用于基于环氧胺双组分反应性体系的反应性粘合剂的反应性组合物的添加剂,其中所述反应性稀释剂单丙烯酸酯b)和环氧胺体系的胺(固化剂)进行反应。
优选地,所述添加剂组合物除了a)和b)之外还包括抑制自由基聚合的稳定剂,其重量含量在10-1000ppm、优选地20-300ppm范围内,相对于a)+b)计。
本发明的第二主题涉及用于制备根据本发明如上限定的二酰胺添加剂组合物的方法,其包括以下相继步骤:
i)将微粒化的粉末形式的所述二酰胺a)在所述稀释剂b)中,在使用温度调节控制的环境温度(即在5-25℃范围内)下,逐渐分散直至获得均匀分散体,
ii)将步骤i)期间获得的均匀分散体在80-100℃范围内的至少一组(set)固定的加热条件下维持1-100小时、优选地10-100小时的时间段,并且所述稀释剂b)没有任何聚合。
术语“环境温度”意指在5-25℃范围内的温度。
所述温度的调节借助通过冷却的调节***进行以避免在微粒化的粉末的分散期间由于剪切产生的加热且避免步骤ii)之前的过早和不受控的活化,其中所述条件最好控制在80-100℃范围内的等温条件下。
更具体地,在步骤ii)结束时,所形成的糊料的根据标准ASTM D 217在如下条件的情况下测量的最大针入值小于15mm、优选地小于10mm:23℃的温度、30度的锥体(cone)、5mm/s测试速度以及0.4N的针入力。
实际上,在步骤ii)结束时,所述添加剂组合物的均匀凝胶或糊料的稠度达到平顶值,之后不会显著改变。
本发明的另一个主题涉及反应性-粘合剂组合物,其包括根据本发明如上限定的或通过根据本发明如上限定的方法获得的至少一种组合物作为流变添加剂。
更具体地,所述反应性粘合剂的反应性组合物为可聚合的、特别是可交联的组合物,其选自涂料组合物特别地选自清漆、涂料、表层凝胶、油漆和墨,或选自胶粘剂或胶组合物,或选自模塑组合物、复合材料组合物、乳香胶组合物、化学锚栓组合物和密封剂组合物,或选自用于立体光刻或用于3D打印制品的可光致交联组合物,特别地通过喷墨来3D打印制品的可光致交联组合物。
其可以是通过自由基途径、或在辐射下、或通过基于过氧化物或氢过氧化物的引发体系可聚合的且特别是可交联的。
在组合物为在UV辐射下可聚合的、特别是可交联的情况下,存在光引发剂。在电子束下,不需要光引发剂。
在使用过氧化物或氢过氧化物引发剂的情形中,可使用分解促进剂。具体地,在氢过氧化物和作为还原剂的分解加快剂的情形中,所述聚合且特别是所述交联可在低温下进行。
甚至更具体地,所述反应性-粘合剂组合物在选自UV、激光、LED和电子束(且优选地UV)的辐射下是可聚合的、特别是可交联的。
根据一个更具体选项,所述单官能的(甲基)丙烯酸类反应性稀释剂b)为在所述预活化的添加剂组合物中的单丙烯酸酯。在该具体情形中,粘合剂的反应性组合物与胺、特别是多胺通过迈克尔加成反应是可聚合的、特别是可交联的。优选地,反应性组合物是可交联的且包括基于环氧树脂和胺(特别是多胺)固化剂的双组分体系。
根据另一具体选项,所述反应性粘合剂的反应性组合物包括至少一种丙烯酸类低聚物和/或至少一种丙烯酸类单体(意指丙烯酸类或甲基丙烯酸类)、和优选地至少一种多官能的丙烯酸类低聚物和/或至少一种多官能的丙烯酸类单体作为所述粘合剂组合物的反应性稀释剂。
根据所述反应性粘合剂组合物的一个具体的可能方案,粘合剂组合物的所述反应性稀释剂为丙烯酸类或甲基丙烯酸类单体,其可与在所述二酰胺添加剂组合物中用作根据b)的反应性稀释剂的单官能的(甲基)丙烯酸类单体相同或不同。
根据本发明如上限定的用作流变添加剂的所述添加剂组合物的重量含量在0.5重量%-10重量%的范围内,相对于所述反应性粘合剂的反应性组合物计。
本发明的最后主题涉及根据本发明如上限定的或通过根据本发明限定的方法获得的添加剂组合物作为粘合剂的反应性组合物的流变添加剂用于即时使用且不需要另外使所述添加剂原位活化的用途。
以下实施例通过阐述本发明和其性能水平的方式给出并且不以任何方式限制其范围。
实验部分
I–使用的起始材料(原料)
表1:使用的起始材料
Figure BDA0001638813790000061
II-使用的方法和试验
包含根据本发明的至少一种添加剂的组合物的流变行为按照以下试验进行表征:
1)稠度
糊料的稠度根据标准ASTM D 217使用变形装置(texturing device)测量。所述标准是指标准化的手动测量装置并且已经通过由Thermorheo(供应商:Swantech)制造的TA-XT2i织构(物性,texture)分析仪再现。所述标准的原理已经在来自Stable Micro Systems的TA-XT2i上自动化。
1)a.原理
使用如标准ASTM D 217中记载的合适锥体,通过给定的力来提供在糊料中的针入值。这种“压痕(indentation)”测量以毫米(mm)计。
耐针入性随稠度而增大,且针入值随该稠度而减小。
1)b.设备
使用的设备如下:
-自动织构分析仪:TA-XT2i,
-锥体,其施加力等于其重量47.5g,具有形成30°角的针,
-针入力:0.4N
-测试速度:5mm/s.
1)c.产物的调理(conditioning)
所测试的产物至少在试验开始之前必须在气候受控的实验室中、在分别23℃和50%RH的温度和相对湿度下调理24小时的时间段。
1)d.产物的制备
将产物在合成之后包装在1升金属筒(高度:13cm,直径:11cm)中。
织构测量在熟化(maturing)阶段之后且在使用样品之前进行。
1)e.步骤
所述试验在气候受控的实验室的温度下进行。在容器上进行三个试验。
将样品放置在椎体下并且将针尖放置在糊料的表面处。
随后启动TA-XT2i上的程序并且触发所述针入。
然后记录针进入糊料中的位移值。
结果以毫米(mm)计。
2)流阻或耐下垂性试验
2)a.原理
该方法专用于测定在没有观察到由于重力引起的任何下垂现象的情况下涂层可施加的最大厚度。
使用术语耐下垂性并且其以μm计。
2)b.装置
所述试验使用下垂试验仪(来自Sheen
Figure BDA0001638813790000081
的整平/下垂试验仪)进行。由不锈钢制成且具有直刮板的所述试验仪包括尺寸(值)递增的切口(V字形切口,notch),其使得可同时施加不同厚度的层。
将所述层施加到具有如下参照物的黑色纸担载体:byko-chart Scrub-testP121-10N,黑色。
2)c.产物的调理
不管配制剂如何,在试验开始之前将待试验的产物在气候受控的实验室中在23℃和50%RH下调理24h。
2)d.步骤
所述试验在气候受控的实验室的温度(23℃和50%RH)下进行。
所述试验包括使用下垂试验仪将厚度不同的油漆的平行带沉积在担载体上。
将所述担载体立即以直立位置放置,其中最薄的膜在顶部。所述带在该处相遇的厚度表示观察到由于重力引起的下垂现象的第一厚度。
耐下垂性性能为未观察到下垂(所述带未相遇)的最大厚度。
其以μm计。
3)粘度
在将所述配制剂调理(参见2)c)之后,如下评价在23℃和50%RH下的
Figure BDA0001638813790000091
粘度
-使用
Figure BDA0001638813790000092
DVI prime–RV粘度计,
-以5个不同的速度:1rpm、5rpm、10rpm、50rpm、100rpm(每分钟的旋转数)。
首先以最慢的速度测量粘度并且通过以递增的方式改变所述速度重复所述操作。
Figure BDA0001638813790000093
粘度以mPa.s计。
III-流变添加剂的制备和表征
1)根据本发明的流变添加剂和对比添加剂的制备
脂肪酸二酰胺的制备
将49.96克六亚甲基二胺(即0.43mol,0.86胺当量)和271.10克12-羟基硬脂酸(即0.86mol,0.86羧基当量)在氮气气氛下引入到装备有温度计、Dean-Stark设备、冷凝器和搅拌机的1升圆底烧瓶中。
将所述混合物始终在氮气流下加热到200℃。从150℃开始,所除去的水开始在Dean Stark设备中积聚。通过酸值和胺值控制所述反应。当酸和胺值(数)小于10mg KOH/g时,将反应混合物冷却到150℃,然后将其排放到有机硅模具中。一旦冷却到环境温度,就将产物通过碾磨机械微粒化并且筛分以获得细的且受控的粒度,其中获得7μm的平均尺寸。
实施例1(本发明):15%的在3,3,5-三甲基环己醇丙烯酸酯(TMCHA)中的预活化的糊料的制备
在环境温度下将150g如上制备的预先碾磨的脂肪酸二酰胺和850g丙烯酸酯单体装填到1升金属筒(canister)(高度:13cm,直径:11cm)中。使用安装有直径4cm的桨叶的
Figure BDA0001638813790000094
CV分散器将2种产物通过经由冷水循环调节温度的不超过20℃的温度下以1500rpm混合15分钟。然后再次将所述筒小心地关闭,并且将其在事先预热到90℃的烘箱中放置24小时。
最终产物为软的白色糊料,其特征在于15%的干活性材料含量和3.00mm的根据标准ASTM D 217测量的耐针入度。
实施例2(本发明):包含20%二酰胺的预活化的糊料的制备,在3,3,5-三甲基环己醇丙烯酸酯(TMCHA)中
在环境温度下将200g如上所述的预先碾磨的脂肪酸二酰胺和800g丙烯酸酯单体装填到1升金属筒(高度:13cm,直径:11cm)中。使用安装有直径4cm的桨叶的
Figure BDA0001638813790000101
CV分散器将2种产物在通过经由冷水循环调节温度的不超过20℃的温度下以1500rpm混合15分钟。然后再次将所述筒小心地关闭并且将其在事先预热到90℃的烘箱中放置24小时。
最终产物为软的白色糊料,其特征在于20%的干活性材料含量和3.00mm的根据标准ASTM D 217测量的耐针入度。
实施例3(对比):在环三羟甲基丙烷缩甲醛丙烯酸酯(CTFA)中的预活化的糊料的制备
在环境温度下将150g如上所述的预先碾磨的脂肪酸二酰胺和850g丙烯酸酯单体装填到1升金属筒(高度:13cm,直径:11cm)中。使用安装有直径4cm的桨叶的
Figure BDA0001638813790000102
CV分散器将2种产物在通过经由冷水循环调节温度的不超过20℃的温度下以1500rpm混合15分钟。然后再次将所述筒小心地关闭,并且将其在事先预热到90℃的烘箱中放置24小时。
最终产物为软的白色糊料,其特征在于15%的干活性材料含量。
实施例4(对比):在三羟甲基丙烷三丙烯酸酯(TMPTA)中的预活化的糊料的制备
在环境温度下将150g如上所述的预先碾磨的脂肪酸二酰胺和850g的丙烯酸酯单体装填到1升金属筒(高度:13cm,直径:11cm)中。使用安装有直径4cm的桨叶的
Figure BDA0001638813790000103
CV分散器将2种产物在通过经由冷水循环调节温度的不超过20℃的温度下以1500rpm混合15分钟。然后再次将所述筒小心地关闭,并且将其在事先预热到90℃的烘箱中放置24小时。
最终产物为软的白色糊料,其特征在于15%的干活性材料含量。
实施例5(对比):在2-苯氧基乙基丙烯酸酯(2-PEA)中的预活化的糊料的制备
在环境温度下将150g如上所述的预先碾磨的脂肪酸二酰胺和850g的丙烯酸酯单体装填到1升金属筒(高度:13cm,直径:11cm)中。使用安装有直径4cm的桨叶的
Figure BDA0001638813790000104
CV分散器将2种产物在通过经由冷水循环调节温度的不超过20℃的温度下以1500rpm混合15分钟。然后再次将所述筒小心地关闭,并且将其在事先预热到90℃的烘箱中放置24小时。
最终产物为软的白色糊料,其特征在于15%的干活性材料含量。
2)根据本发明的流变添加剂和对比添加剂的表征
在可光致交联的涂料配制剂和2-组分配制剂的制备中在不使用溶剂的情况下使用预活化的糊料形式的流变添加剂。
将流变添加剂用于可光致交联的配制剂
涂料配制剂的制造
通过装备有反絮凝机的
Figure BDA0001638813790000111
AE型高速分散器在实验室中制造涂料配制剂。
将丙烯酸酯低聚物树脂(CN203)和反应性稀释剂(反应性粘合剂的配制剂单体)丙氧基化的(3)三丙烯酸甘油酯(即每个分子带有3个丙氧基单元)(GPTA–SR 9020)以1000rpm、在2m/s切向速度下混合5分钟。
然后加入流变添加剂,并且将其以1500rpm分散20分钟。
所述低聚物和所述反应性稀释剂之间的交联反应在UV灯下通过期间通过UV辐射的作用借助于所述可光致交联的涂料配制剂中所包含的引发剂进行。
表征试验在23℃和50%RH下调理之后在制备配制剂之后的24小时之内进行。
制备了可交联涂料组合物的六个简化配方:
-实施例6:不具有添加剂的配方。
-实施例7:具有添加剂
Figure BDA0001638813790000112
PA4X20的配方(二甲苯-非-反应性溶剂中20%的活性材料)。
-实施例8:具有实施例1中所描述的添加剂的配方(根据本发明的包含脂环族结构的单官能的反应性稀释剂中15%的活性材料)。
-实施例9:具有实施例2中所描述的添加剂的配方(根据本发明的包含脂环族结构的单官能的反应性稀释剂中20%的活性材料)。
-实施例10:具有实施例3中所描述的添加剂配方(对比的杂环的单官能的反应性稀释剂中15%的活性材料).
-实施例11:具有实施例4中所描述的添加剂的配方(对比的三官能的反应性稀释剂中15%的活性材料)。
-实施例12:具有实施例5中所描述的添加剂的配方(对比的芳族的单官能的反应性稀释剂中15%的活性材料)。
根据以下配方制备6个实施例(参见表2):
表2
Figure BDA0001638813790000121
结果
表3
Figure BDA0001638813790000131
将流变添加剂在不使用溶剂的情况下用于环氧配制剂
涂料配制剂的制造
在实验室中以2步制造涂料配制剂。
第一步包括配制称为“部分A”的混合物,其为填料在环氧树脂中的分散体。还将流变添加剂加入到部分A。第二步为以计算的比率将称为“部分B”的氨基固化剂加入到所述部分A以调节交联反应性。
涂料的交联反应通过包含环氧树脂的部分A和包含氨基固化剂的部分B的反应提供。
在实验室中,通过装备有反絮凝机的Dispermat AE型高速分散器制造部分A。
将环氧树脂–DER 324、填料(二氧化钛、磷酸锌、滑石)和消泡剂以3000rpm在6m/s的切向速度下混合30分钟。
然后将流变添加剂加入到所述部分A并且将其以1500rpm分散20分钟。
在静置24h之后,将部分B与部分A以1500rpm混合2分钟。
然后,在随后的30分钟内进行表征试验。
制备了不具有溶剂和包括两种组分(环氧/胺)的三个环氧涂料配方:
-实施例13:不具有添加剂的配方。
-实施例14:具有实施例1中所描述的添加剂的配方。
-实施例15:具有实施例2中所描述的添加剂的配方。
表4
Figure BDA0001638813790000141
(*)对比实施例13的配制剂包括5.6份单体反应性稀释剂以使其处于可与实施例14和15严格对比的条件下。
结果
表5
Figure BDA0001638813790000142
Figure BDA0001638813790000151

Claims (24)

1.基于脂肪酸二酰胺的流变添加剂组合物,其中所述组合物的脂肪酸二酰胺为已经预活化和预浓缩的并且所述组合物包括:
a)5重量%-30重量%的基于12-羟基硬脂酸和线型的C5、C6或C7的脂族二胺的至少一种脂肪酸二酰胺,
b)70重量%-95重量%的包含一个脂环族基团或多个脂环族基团的至少一种单官能的(甲基)丙烯酸类反应性稀释剂,所述脂环族基团可被至少一个C1-C4烷基所取代,
所述%相对于a)+b)计。
2.权利要求1的组合物,其中所述二胺为C6线型脂族二胺。
3.权利要求1的组合物,其中相对于a)+b)计,所述二酰胺以10%-25%范围内的重量含量存在且所述稀释剂b)以75%-90%范围内的重量含量存在。
4.权利要求1的组合物,其中所述单官能的(甲基)丙烯酸类单体反应性稀释剂b)选自:二环戊二烯基(甲基)丙烯酸酯、降冰片基(甲基)丙烯酸酯、异冰片基(甲基)丙烯酸酯(IBO(M)A)、叔丁基环己醇(甲基)丙烯酸酯(TBCH(M)A)、三环癸烷二醇单(甲基)丙烯酸酯或3,3,5-三甲基环己醇(甲基)丙烯酸酯(TMCH(M)A)。
5.权利要求1的组合物,其中所述单官能的(甲基)丙烯酸类单体反应性稀释剂b)为单丙烯酸酯。
6.权利要求1的组合物,其中其除了a)和b)之外还包括抑制自由基聚合的稳定剂,其重量含量相对于a)+b)计在10-1000ppm范围内。
7.一种用于制备如根据权利要求1限定的二酰胺添加剂组合物的方法,其中其包括以下相继步骤:
i)将微粒化的粉末形式的所述二酰胺a)在所述稀释剂b)中,在使用温度调节控制的在5-25℃范围内的环境温度下,逐渐分散直至获得均匀分散体,
ii)将步骤i)期间获得的均匀分散体在至少一组在80-100℃范围内的固定加热条件下维持1-100小时的时间段,并且所述稀释剂b)没有任何聚合。
8.根据权利要求7所述的方法,其中,在步骤ii)结束时,所形成的糊料的根据标准ASTMD 217测量的最大针入值小于15mm。
9.反应性-粘合剂组合物,其中其包括如根据权利要求1限定的或通过如根据权利要求7限定的方法获得的至少一种组合物作为流变添加剂。
10.权利要求9的反应性-粘合剂组合物,其中所述反应性-粘合剂组合物是可聚合的组合物,其选自复合材料组合物。
11.权利要求10的反应性-粘合剂组合物,其中所述反应性-粘合剂组合物是可聚合的组合物,其选自涂料组合物,胶组合物,模塑组合物,化学锚栓组合物,密封剂组合物,或者用于立体光刻或用于3D打印制品的可光致交联组合物。
12.权利要求10的反应性-粘合剂组合物,其中所述反应性-粘合剂组合物是可聚合的组合物,其选自胶粘剂,乳香胶组合物。
13.权利要求9的反应性-粘合剂组合物,其中所述反应性-粘合剂组合物在辐射下或通过基于过氧化物的引发体系可通过自由基途径交联。
14.权利要求13的反应性-粘合剂组合物,其中所述引发体系是基于氢过氧化物的。
15.权利要求10的反应性-粘合剂组合物,其中所述反应性-粘合剂组合物在选自UV、激光、LED和电子束的辐射下是可聚合的。
16.权利要求9的反应性-粘合剂组合物,其中所述单官能的(甲基)丙烯酸类反应性稀释剂b)是如根据权利要求5限定的单丙烯酸酯。
17.权利要求16的反应性-粘合剂组合物,其中所述反应性-粘合剂组合物与胺通过迈克尔加成反应是可聚合的。
18.权利要求9的反应性-粘合剂组合物,其中所述反应性-粘合剂组合物是可交联的且包括基于环氧树脂和胺固化剂的双组分体系。
19.权利要求9的反应性-粘合剂组合物,其中所述反应性-粘合剂组合物包括至少一种丙烯酸类低聚物和/或至少一种丙烯酸类单体作为所述粘合剂组合物的反应性稀释剂。
20.权利要求9的反应性-粘合剂组合物,其中用作流变添加剂的根据权利要求1的所述组合物的重量含量在0.5重量%-10重量%的范围内,相对于所述反应性-粘合剂组合物计。
21.制备用于即时使用的反应性粘合剂组合物的方法,其中所述方法包括使用权利要求1的组合物或通过权利要求7的方法获得的组合物作为流变添加剂且不需要使所述流变添加剂另外原位活化。
22.权利要求21的方法,其中反应性粘合剂的所述反应性组合物为可聚合的组合物,其选自复合材料组合物。
23.权利要求22的反应性-粘合剂组合物,其中所述反应性-粘合剂组合物是可聚合的组合物,其选自涂料组合物,胶组合物,模塑组合物,化学锚栓组合物,密封剂组合物,或者用于立体光刻或用于3D打印制品的可光致交联组合物。
24.权利要求22的反应性-粘合剂组合物,其中所述反应性-粘合剂组合物是可聚合的组合物,其选自胶粘剂,乳香胶组合物。
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