CN102421834A - 塑料模塑料及其制备方法 - Google Patents
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Abstract
塑料模塑料，其包含选自氰酸酯树脂、环氧-线型酚醛树脂、多官能环氧树脂、双马来酰亚胺树脂和它们的混合物的聚合物树脂以及至少一种填料，其特征在于，基于塑料模塑料的总重量计，在所述塑料模塑料中填料的比例为65-92重量％。
Description
现有技术
本发明涉及一种根据权利要求1的前叙部分包含聚合物树脂的塑料模塑料。本发明还涉及制备此种塑料模塑料的方法以及由此种塑料模塑料制备模制品的方法。
含有选自氰酸酯树脂、环氧-线型酚醛树脂、多官能的环氧树脂、双马来酰亚胺树脂和它们的混合物的聚合物树脂以及至少一种填料的塑料模塑料能够用于例如高温，特别是高于100℃温度的应用。这样的应用领域包括例如汽车的发动机舱。在现代的汽车发动机舱中包含了一系列的电气和电子元件。其相应的连接件，例如插头、开关或壳体，必须能够承受汽车发动机舱中的温度。这样就要求使用易于加工、价格便宜而又具有绝缘性能的材料。
目前用于这种用途的塑料模塑料通常具有最高达180℃的连续耐高温性。由于发动机密封性增加和发动机运行的工作温度提高，提高了汽车发动机舱中的应用温度。但是已知的现在用于生产壳体、插头和外罩的塑料模塑料已无法应付发动机舱升高的温度。
本发明的公开
根据本发明的塑料模塑料包含聚合物树脂以及至少一种填料，所述聚合物树脂选自氰酸酯树脂、环氧-线型酚醛树脂、多官能的环氧树脂、双马来酰亚胺树脂和它们的混合物，其中在此种塑料模塑料中，填料占塑料模塑料总重量的65-92重量％。
通过应用氰酸酯树脂、环氧-线型酚醛树脂、多官能的环氧树脂、双马来酰亚胺树脂或它们的混合物以及65-92重量％的高填料比例得到一种塑料模塑料，其连续耐高温性相对于已知的塑料模塑料明显提高。因此根据本发明的塑料模塑料的应用范围例如在连续负荷时可为温度最高达300℃以及任选地甚至温度最高达380℃。
适于这种塑料模塑料的氰酸酯树脂是例如聚苯酚氰酸酯，特别是低聚（3-亚甲基-1,5-亚苯基氰酸酯），基于线型酚醛树脂的氰酸酯，基于二苯乙烷-4,4-二氰酸酯的氰酸酯，基于亚乙基-双-4,1-苯基二氰酸酯的氰酸酯或者至少两种这些树脂的混合物。
此外，氰酸酯树脂可以与环氧树脂，例如基于双酚A或双酚F的环氧树脂和/或与脂环族的环氧树脂混合。多官能的环氧树脂可以单独或者与一种或多种氰酸酯混合或者与双马来酰亚胺混合含于聚合物树脂中，其尤其为三或四官能的环氧树脂。特别合适的多官能环氧树脂是N,N,N',N'-四缩水甘油基-4,4'-亚甲基双苯胺和/或三缩水甘油化的对氨基苯酚。
由于其热固性结构，根据本发明使用的聚合物树脂即使在高温下也基本上是形状稳定的，只要该高温低于聚合物树脂的分解温度。
根据本发明，塑料模塑料含有分别基于塑料模塑料总重量计为65-92重量％，优选70-90重量％和特别为75-78重量％的至少一种填料。包含在模塑料中的填料选自玻璃纤维、结晶石英、无定形石英、氧化铝、碳酸钙、硅灰石、滑石、云母、氮化硼、碳化硅、碳纤维、有/或没有涂层的银和它们的混合物。
如果作为填料使用玻璃纤维，则优选使用短玻璃纤维。短玻璃纤维的直径优选为5-15μm。但是短玻璃纤维也可用长度为2-7mm，特别是长度为3-4mm且直径为8-12μm的长玻璃纤维替代使用。这里玻璃纤维的长度分别这样测量，即可以将它们与作为制备塑料模塑料的原料使用的单体单元和低聚物单元均匀地混合。
如果作为填料使用无定形石英，则其可以为有粉碎的或球形形式或者粉碎的和球形的颗粒的混合物形式。如果作为填料使用的银颗粒具有涂层，则涂层优选选自硅烷。通过涂层，得到在聚合物树脂基体中提高的颗粒连接。
除了通常的颗粒尺寸，作为填料使用的材料此外也可以使用纳米级的填料颗粒。适合的纳米级的填料为例如碳纳米管或碳纳米纤维。
根据本发明所述塑料模塑料可含有一种填料或含有两种或更多种填料的混合物。如果含有两种或更多种填料，则同样的材料可以使用不同的颗粒大小、规格和/或颗粒形状，或者使用不同材料的填料。它们可以具有相同的或相似的形状或者其形状和尺寸各不相同。也可同时使用常规颗粒大小的填料和纳米级的填料。在此任意混合比例都是可能的。
特别优选作为根据本发明的塑料模塑料的填料使用无定形石英和/或氧化铝。
除了聚合物树脂和填料之外，塑料模塑料也可以包含其它的成分和添加剂。
可以例如在塑料模塑料中加入0-14重量％、优选1-3重量％的基于氰酸酯或多官能环氧树脂的硅酮改性剂。
通过加入基于氰酸酯或多官能环氧树脂的硅酮改性剂可使塑料模塑料的性质适应于预计用途。可通过加入硅酮改性剂改变的性质是例如断裂力学性质如断裂伸长，耐温度交变性能，撕裂扩展抗力。
作为硅酮改性剂适合的例如为低粘度的聚有机硅橡胶改性的氰酸酯。
其它可在模塑料中包含的添加剂为例如沉淀抑制剂、交联助剂、流动助剂或粘合促进剂。添加剂可以单独地或组合地使用。通常使用的添加剂的比例为0.5-3重量％。添加剂在塑料模塑料中的总比例优选为0.5-1.5重量％。
例如蒙脱石、无定形氧化硅或热解二氧化硅适合作为沉淀抑制剂。其中热解二氧化硅特别优选。
通常使用的交联助剂是例如盐溶液或酸性聚酯的溶液。优选酸性聚酯的溶液。
作为流动助剂适合的为例如酸性聚酯的溶液。
作为粘合促进剂适合的例如是硅烷。
除上述添加剂之外或替代上述添加剂也可在塑料模塑料中含有色料和/或稳定剂。如果使用色料，则可使用有机或无机颜料。此处优选使用无机颜料。
本发明此外还涉及制备此种塑料模塑料的方法。此方法包含如下步骤：
（a）将树脂成分预热至40-80℃的温度范围，
（b）加入预热的填料，直到填充度达到55-65重量％，
（c）任选地加入其它填料至捏合机、辊轧单元/压板单元、二辊轧机和/或压延机中，
（d）在填充度达到至少55重量％后加入催化剂。
通过根据本发明的方法得到的塑料模塑料即使在温度高于180℃时也形状稳定。
为生产塑料模塑料使用的树脂成分可以是单体单元、低聚物或预制的聚合物材料。通常使用单体单元或低聚物单元或只是部分交联的聚合物单元。通常用于制备氰酸酯树脂使用的树脂成分是例如低聚（3-亚甲基-1,5-亚乙基氰酸酯），二苯乙烷-4,4-二氰酸酯或乙叉-双-4,1-苯基二氰酸酯。为了制备聚合物树脂，通常额外加入固化剂。如果应该制备由两种不同的氰酸酯或一种氰酸酯和一种环氧树脂和/或一种双马来酰亚胺树脂的混合物，则每种树脂原料可以一起加入或者使各自部分交联的基质相互混合。加入各自的粘结剂和固化剂（通常为单体单元形式）时，则除了聚合物共混物外也可以制得共聚物。
取决于使用的树脂和树脂成分的加工步骤，例如树脂成分是作为单体单元还是作为已经预聚合的单元使用，可将树脂成分直接加入溶解器中或者必须使其事先熔融。如果树脂成分必须事先熔融，则先将其加热至熔解温度。然后与填料的混合在高于熔解温度的温度下进行。
用于生产聚合物树脂的树脂成分优选在真空下在溶解器中混合。如果塑料模塑料中应该另外加入添加剂，则将这些添加剂与树脂成分一起加入溶解器中。加入预热过的填料直至填充度达到55-70重量％也同样在溶解器中进行。再将如此备料的混合物加入捏合机，例如西格玛捏合机，辊轧单元/压板单元，二辊轧机和/或压延机中。然后在捏合机、辊轧单元/压板单元、二辊轧机和/或压延机中可加入其它填料。此外，为引发聚合反应而引入催化剂。这里根据本发明，催化剂的加入是在填充度达到至少55重量％时才进行。如果填料在塑料模塑料中的比例大于70重量％，优选催化剂的加入在填充度达到至少70重量％时才进行。这里填充度是指在塑料模塑料中的填料量。
例如金属盐、胺或路易斯酸适合作为使用的催化剂。合适的金属盐为例如锰、铜、钴或锌的乙酰丙酮化物、环烷酸盐、辛酸盐或羧酸盐。双酚F或A环氧树脂也适合。作为胺适合的是例如双氰胺。
能够作为催化剂使用的合适的路易斯酸是例如B(CH3)3，BF3，AlCl3或FeCl3。
模塑料制备以后优选在粉碎过程中进一步加工成粒料。也可以由压制过程制成塑料模塑料的粒料。
或者也可以将这样制备的模塑料直接用于待制备零件的模制过程。
通过本发明的方法制备的根据本发明的模塑料在室温下的弹性模量为10000-15000n/mm2。这样制备的塑料模塑料的玻璃转化温度为180-300℃。这样制备的根据本发明的塑料模塑料的热膨胀系数α为9-14·10-61/℃。此外。这种塑料模塑料的断裂应力为90-120N/mm2，断裂伸长率为0.8-1.5％。
通过根据本发明的方法制备模塑料后可以由该塑料模塑料制备模制品。该模制品的生产既可以由之前制备的粒料或粒状物也可以在制备模塑料后直接由所制备的模塑料进行。模制品的制备包括如下步骤：
（a）在120-250℃的温度，25-200巴的压力，20秒-10分钟的保压时间条件下由模塑料生产模制品，
（b）在200-300℃的温度和10-120分钟的保压时间条件下后固化模制品。
为生产模制品将模塑料在压力下注射入具有120-250℃温度的工具中。此处的压力在前述的25-200巴范围内。为注射使用例如塑料注射成型机或者任意其它本专业技术人员已知的注射装置。
在加热模型中的保压时间之后将模制品取出，在200-300℃温度范围内再放置10-120分钟。放置可例如在合适的烘箱中或合适的加热箱中进行。烘箱的加热通常用电进行。
通过根据本发明的方法可以生产例如构件，其适于包覆受到高热应力的电气或电子部件。这种电气或电子部件为例如插座连接、控制单元（如用于汽车发动机舱中）或者光致发热体应用的逆变器。
Claims (12)
1.塑料模塑料，其包含选自氰酸酯树脂、环氧-线型酚醛树脂、多官能环氧树脂、双马来酰亚胺树脂和它们的混合物的聚合物树脂以及至少一种填料，其特征在于，基于塑料模塑料总重量计，填料在塑料模塑料中的比例为65-92重量％。
2.根据权利要求1的塑料模塑料，其特征在于，氰酸酯树脂为聚氰酸苯酚酯，基于线型酚醛树脂的氰酸酯，基于二苯乙烷-4,4-二氰酸酯的氰酸酯，基于乙叉-双-4,1-苯基二氰酸酯的氰酸酯或者至少两种这些树脂的混合物。
3.根据权利要求1或2的塑料模塑料，其特征在于，所述氰酸酯与基于双酚A或双酚F的环氧树脂和/或与脂环族环氧树脂混合。
4.根据权利要求1至3之一的塑料模塑料，其特征在于，所述多官能环氧树脂是三或四官能的环氧树脂。
5.根据权利要求1至4之一的塑料模塑料，其特征在于，所述填料选自玻璃纤维、结晶石英、无定形石英、氧化铝、碳酸钙、硅灰石、滑石、云母、氮化硼、碳化硅、碳纤维、有/或没有涂层的银和它们的混合物。
6.根据权利要求1至5之一的塑料模塑料，其特征在于还含有比例为0-14重量％的基于氰酸酯或多官能环氧树脂的硅酮改性剂。
7.根据权利要求1至6之一的塑料模塑料，其特征在于，在该模塑料中包含沉淀抑制剂、交联助剂、流动助剂或粘合促进剂。
8.制备根据权利要求1至7之一的塑料模塑料的方法，包括如下步骤：
（a）将树脂成分预热至40-80℃的温度范围，
（b）加入经预热的填料，直到填充度达到55-65重量％，
（c）任选地加入其它填料至捏合机、辊轧单元/压板单元、二辊轧机和/或压延机中，
（d）在填充度达到至少55重量％后加入催化剂。
9.根据权利要求8的方法，其特征在于，所述催化剂选自金属盐、胺、路易斯酸和双酚F或A环氧树脂。
10.根据权利要求9的方法，其特征在于，所述金属盐为锰、铜、钴或锌的乙酰丙酮化物、环烷酸盐、辛酸盐或羧酸盐。
11.根据权利要求9的方法，其特征在于，所述胺是双氰胺。
12.由根据权利要求1至7之一的塑料模塑料生产模塑件的方法，包括如下步骤：
（a）在120-250℃的温度，25-200巴的压力，在模中保压时间为20秒-10分钟的条件下由所述模塑料生产模塑件，
（b）在200-300℃的温度和10-120分钟的保压时间条件下对所述模塑件进行后固化。
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| CN115087688A (zh) * | 2020-02-14 | 2022-09-20 | 阿尔萨达股份公司 | 由块状模塑料制备模塑复合材料的方法 |
| CN115087688B (zh) * | 2020-02-14 | 2024-04-26 | 阿尔萨达股份公司 | 由块状模塑料制备模塑复合材料的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120027236A (ko) | 2012-03-21 |
| US20120153532A1 (en) | 2012-06-21 |
| JP2012526871A (ja) | 2012-11-01 |
| WO2010130507A1 (de) | 2010-11-18 |
| EP2430087A1 (de) | 2012-03-21 |
| CN102421834B (zh) | 2014-12-10 |
| DE102009003132A1 (de) | 2010-11-18 |
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