CN108136683A - 焊接聚酰胺和聚(甲基)丙烯酸酯塑料的方法 - Google Patents

焊接聚酰胺和聚(甲基)丙烯酸酯塑料的方法 Download PDF

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CN108136683A
CN108136683A CN201680060616.5A CN201680060616A CN108136683A CN 108136683 A CN108136683 A CN 108136683A CN 201680060616 A CN201680060616 A CN 201680060616A CN 108136683 A CN108136683 A CN 108136683A
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Prior art keywords
weight
priming paint
poly
methyl
polyamide
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Inventor
P·沃尔特
N·费里德里克
L·冈萨雷斯
H·吕岑
T·黑蒂希
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of CN108136683A publication Critical patent/CN108136683A/zh
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Abstract

本发明涉及一种采用底漆焊接聚酰胺塑料和聚(甲基)丙烯酸酯塑料的方法，所述聚(甲基)丙烯酸酯特别是聚甲基丙烯酸甲酯，所述底漆包含至少一种由至少一种苯乙烯或苯乙烯衍生物与至少一种马来酸酐或马来酸酐衍生物合成的共聚物。本发明还涉及相应的焊接产品。

Description

焊接聚酰胺和聚(甲基)丙烯酸酯塑料的方法
本发明涉及一种采用底漆焊接聚酰胺塑料和聚(甲基)丙烯酸酯塑料的方法，所述底漆包含至少一种由至少一种苯乙烯或苯乙烯衍生物与至少一种马来酸酐或马来酸酐衍生物合成的共聚物。本发明还涉及相应的焊接产品。
现有技术中已知各种将两种或更多种由塑料材料构成的基板相互连接的方法，所述塑料材料，例如聚烯烃、聚丙烯酸酯或聚酰胺。在这种情况下，既有机械连接选择，例如锁接或螺接，也有粘合剂粘结方法。作为替代，也可以将塑料材料焊接在一起。焊接是不可拆卸地、整体地、物理地连接塑料材料的结合方法，所述塑料材料通常是相同类型的，例如PE和PE，或PA和PA。相同类型的热塑性材料是在它们的分子结构、它们的熔点、它们的熔融粘度和它们的热膨胀系数方面相差不大的聚合物，并且原则上它们在一定程度上可以彼此混合。相同类型的塑料材料通常是具有相同聚合物基底和/或相同塑料的塑料材料。
已知许多将两种或更多种相同类型的塑料材料焊接在一起的方法。在这种情况下，可以采用各种焊接方法，例如红外焊接，红外/摩擦焊接或超声焊接。这些焊接相同类型的塑料材料的方法基于相关的塑料材料在焊接区的区域中熔化，并且材料在该区域中以整体粘结和摩擦的方式彼此连接。
如果准备将相同类型的塑料材料相互连接，那么这些焊接方法的效果很好。但是，一旦准备将两种不同类型的和/或互相不相容的塑料材料焊接在一起，所述塑料材料例如聚酰胺和聚(甲基)丙烯酸酯塑料，不可能在两个基板之间制备出具有足够高的机械强度的持久连接。如果尝试采用现有技术中已知的焊接方法直接焊接两种塑料，即，聚酰胺和聚(甲基)丙烯酸酯，或者更明确地，聚酰胺和聚(甲基丙烯酸甲酯)，不能获得强度或者只能获得非常低的强度。
迄今为止，只能通过机械连接或者粘合剂粘结方法将相应的不同的塑料材料互相连接。机械连接的缺点是复杂的附件、准确的材料应力和需要使用额外的机械连接装置。而且，在机械连接的情况下，很少能实现整体连接。但是，粘合剂粘结方法的缺点是，只能在很长时间之后，可能是长达几周之后，才能实现最终的连接强度。而且，粘合剂粘结低能表面通常需要对结合配件进行费力的预处理。而且，因为室外气候条件，粘合剂粘结经常不确定地不稳定。另外，提供清洁的粘合剂粘结经常是复杂和费时的。因此，对于塑料材料，通过焊接方法进行连接是最清洁、最快速和最简单的解决办法。
因此，本发明的目的是提供焊接聚酰胺塑料和聚(甲基)丙烯酸酯塑料的简单方法，聚(甲基)丙烯酸酯特别是聚(甲基丙烯酸甲酯)。在这种情况下，期望通过焊缝在所述不同塑料材料之间进行的连接是尽可能稳定和持久的。
已经令人惊奇地发现，通过采用底漆焊接聚酰胺塑料和聚(甲基)丙烯酸酯塑料的方法实现了该目的，所述聚(甲基)丙烯酸酯特别是聚(甲基丙烯酸甲酯)，其中所述底漆包含至少一种由至少一种苯乙烯或苯乙烯衍生物与至少一种马来酸酐或马来酸酐衍生物合成的共聚物。
当焊接聚酰胺塑料和聚(甲基丙烯酸甲酯)塑料时，采用包含至少一种相应的共聚物的底漆已经可以在塑料材料之间实现特别稳定和不老化的连接。
采用底漆待焊接的第一结合配件(join partner)是聚酰胺塑料。聚酰胺塑料优选是热塑性聚酰胺。基于酰胺的热塑性聚合物包括，例如，聚酰胺6、ε-己内酰胺的均聚物(聚己内酰胺)；聚酰胺11、11-氨基十一酸的缩聚物聚(11-氨基十一酰胺)；聚酰胺12、ω-十二内酰胺的均聚物(聚十二内酰胺)；聚酰胺6.6、六亚甲基二胺与己二酸的均相缩聚物(聚己二酰己二胺)；聚酰胺6.10、六亚甲基二胺与癸二酸的均相缩聚物(聚(癸二酰己二胺))；聚酰胺6.12、六亚甲基二胺与十二烷二酸的均相缩聚物(聚十二烷二酰己二胺),或聚酰胺6-3-T、三甲基六亚甲基二胺与对苯二甲酸的均相缩聚物(聚三甲基六亚甲基二胺)、苯二胺与对苯二甲酸的聚(对苯二甲酰对苯二胺)或聚(对苯二甲酰间苯二胺)、不同二胺与对苯二甲酸的聚邻苯二甲酰胺(PPA)、及它们的混合物。
光学透明的聚酰胺包括包含线性脂肪族二羧酸和脂环族二胺的单晶聚酰胺、包含线性脂肪族二羧酸和脂环族二胺和任选存在的内酰胺或氨基酸的无定形聚酰胺、包含对苯二甲酸和脂环族或支化脂肪族二胺和任选存在的内酰胺或氨基酸的无定形聚酰胺、或包含间苯二甲酸和脂环族或线性或支化脂肪族二胺和任选存在的内酰胺或氨基酸的无定形聚酰胺。合适的光学透明的聚酰胺是，例如，十二烷二酸与4,4’-二氨基二环己基甲烷的异构体的混合物的酰胺，对苯二甲酸与2,2,4-三甲基六亚甲基二胺和2,4,4-三甲基六亚甲基二胺的异构体的混合物的酰胺，十二烷二酸与3,3’-二甲基-4,4’-二(氨基环己基)-甲烷的异构体的混合物的酰胺，十二内酰胺、间苯二甲酸与3,3’-二甲基-4,4’-二(氨基环己基)-甲烷的异构体的混合物的酰胺，或十四烷二酸与3,3’-二甲基-4,4’-二(氨基环己基)-甲烷的异构体的混合物的酰胺或ε-己内酰胺的酰胺或ω-十二内酰胺的酰胺。
优选的聚酰胺选自聚酰胺6、聚酰胺6.6、聚酰胺6.10、聚酰胺6.12、聚酰胺10.10、聚酰胺11、聚酰胺12、聚酰胺10.12、聚邻苯二甲酰胺、光学透明的聚酰胺或基于所述聚酰胺的混合物。特别优选的聚酰胺选自聚酰胺6、聚酰胺6.6、聚酰胺12、聚邻苯二甲酰胺、光学透明的聚酰胺和它们的混合物，特别是聚酰胺12、聚酰胺6、聚酰胺6.6和它们的混合物。聚酰胺塑料也可以包含另外的组分，例如填料例如玻璃纤维、颜料、矿物颗粒、染料、流变助剂、脱膜助剂或稳定剂。在每种情况下，基于总的聚酰胺塑料(包括填料)，聚酰胺塑料优选包含大于40重量％，特别是大于60重量％，优选大于70重量％，优选大于90重量％的所提及的聚酰胺。在每种情况下，基于聚酰胺塑料(总聚酰胺塑料，不含填料)的总聚合物含量，聚酰胺塑料优选包含大于90重量％，特别是大于95重量％，优选大于98重量％的所提及的聚酰胺。在每种情况下，基于总聚酰胺塑料(包括填料)，聚酰胺塑料优选具有的所提及的聚酰胺的含量为50-90重量％，特别是60-80重量％。
聚(甲基)丙烯酸酯是合成的、优选是透明的热塑性材料。优选的聚(甲基)丙烯酸酯包含50-100重量％，特别是70-100重量％的丙烯酸酯和/或甲基丙烯酸酯，(甲基)丙烯酸酯单元优选被C1-C12烷基官能团，特别是C1-C4，优选甲基官能团酯化。聚(甲基)丙烯酸酯的书写形式表明聚合物由丙烯酸酯和/或甲基丙烯酸酯组成。换句话说，书面形式的(甲基)丙烯酸酯表明它可以是丙烯酸酯和甲基丙烯酸酯。特别优选聚(甲基)丙烯酸酯是聚(甲基丙烯酸甲酯)(PMMA，也俗称丙烯酸玻璃或树脂玻璃(Plexiglas))。优选的聚(甲基丙烯酸甲酯)包含50-100重量％，特别是70-100重量％的甲基丙烯酸甲酯。
基本地，(甲基)丙烯酸，特别是丙烯酸，以及它们的在烷基官能团中具有1-12个碳原子特别是1-4个碳原子的烷基酯，以及丙烯腈和/或甲基丙烯腈，丙烯酰胺和/或甲基丙烯酰胺，苯乙烯和/或马来酸酐可以作为构成聚(甲基)丙烯酸酯，特别是聚(甲基丙烯酸甲酯)的共聚单体。优选热塑性和热弹性的可变形塑料材料。优选的热塑性聚(甲基丙烯酸甲酯)塑料的重均摩尔质量(重均分子量)大于50000g/mol，特别是大于100000g/mol。热塑性聚(甲基)丙烯酸酯塑料，特别是聚(甲基丙烯酸甲酯)塑料的优选的重均摩尔质量(重均分子量)小于2000000g/mol，特别是小于1000000g/mol，优选小于500000g/mol。特别优选的热塑性聚(甲基)丙烯酸酯塑料，特别是聚(甲基丙烯酸甲酯)塑料的重均摩尔质量(重均分子量)为50000g/mol至250000g/mol，例如约100000g/mol至约180000g/mol，以便用于注塑。
聚(甲基)丙烯酸酯塑料，特别是聚(甲基丙烯酸甲酯)塑料也可以含有另外的组分，例如填料例如玻璃纤维、颜料、染料、流变助剂、脱膜助剂或稳定剂。在每种情况下，基于聚(甲基)丙烯酸酯塑料的聚合物含量(总聚(甲基)丙烯酸酯塑料，不含填料)，聚(甲基)丙烯酸酯塑料，特别是聚(甲基丙烯酸甲酯)塑料优选包含大于90重量％，特别是大于95重量％，优选大于98重量％的所提及的聚(甲基)丙烯酸酯，特别是所提及的聚(甲基丙烯酸甲酯)。在每种情况下，基于总聚(甲基)丙烯酸酯塑料(包括填料)，聚(甲基丙烯酸甲酯)塑料优选包含大于90重量％，特别是大于95重量％，优选大于98重量％的所提及的聚(甲基)丙烯酸酯，特别是所提及的聚(甲基丙烯酸甲酯)。
本发明的另一个重要部分是至少一种底漆的用途，优选刚好一种底漆的用途。底漆包含至少一种共聚物，所述至少一种共聚物包含至少一种苯乙烯或苯乙烯衍生物和至少一种马来酸酐或马来酸酐衍生物作为通过聚合并入的单体。
底漆是焊接助剂，其优选作为预处理层，在结合区的区域内施加于待焊接的基板表面中的至少一个。底漆不应理解为粘合剂、清洁剂或类似物，与之相对地，底漆是焊接助剂，其使得结合配件在结合区(或焊接区)彼此相容，从而通过结合，在结合区实现了待焊接基板之间的整体结合和摩擦连接。
测试已经显示采用包含根据本发明的共聚物的相应的底漆可以使塑料，即，聚酰胺和聚(甲基)丙烯酸酯，通过焊接在接缝处相容，因此可以实现稳定和持久的连接。如果不使用相应的底漆，不能实现焊接连接的强度或者只能实现非常低强度的焊接连接。优选地，结合的基板的拉伸强度大于2MPa，特别是大于4MPa。以5mm/s的牵引速度并且根据测试中描述的测试实施来测定拉伸强度。
优选地，至少由苯乙烯单体和马来酸酐单体来合成底漆中的至少一种第一共聚物。除了苯乙烯或苯乙烯衍生物(例如α-甲基苯乙烯)和马来酸酐或马来酸酐衍生物之外，共聚物还可以包含通过聚合并入的另外的单体。共聚物优选包含选自丙烯酸酯和甲基丙烯酸酯(合在一起为(甲基)丙烯酸酯)的单体，特别是包含具有1-12个碳原子优选1-4个碳原子的烷基官能团的(甲基)丙烯酸酯，优选(甲基)丙烯酸甲酯。而且，也可以采用具有官能性的官能单体，官能性例如环氧化物或异氰酸酯基团，羧基或胺基团，以及烷氧基硅烷基团。
在具体实施方式中，共聚物由通过聚合并入的苯乙烯和马来酸酐组成。在另外的具体实施方式中，共聚物由通过聚合并入的苯乙烯、马来酸酐和甲基丙烯酸甲酯组成。可以不同的摩尔比和这些变体的形式使用单体。
在根据本发明的共聚物的优选实施方式中，苯乙烯与马来酸酐的摩尔比为1:0.01-1:2，优选1:0.05-1:1，特别优选1:0.1-1:0.3。在包含通过聚合并入的丙烯酸酯和/或甲基丙烯酸酯的根据本发明的共聚物的另外的优选实施方式中，丙烯酸酯和/或甲基丙烯酸酯特别是丙烯酸甲酯和/或甲基丙烯酸甲酯，苯乙烯：(甲基)丙烯酸酯：马来酸酐的摩尔比为1:5:2-1:0.2:0.01，特别是1:2:1-1:0.5:0.05，优选1:1.5:0.5-1:0.8:0.1，特别优选1:1:0.2。
可以已知方式由单体合成共聚物。而且，共聚物可以在类似聚合物的反应中进行接枝。用于接枝的特别优选的反应物有醇、硫醇、胺、异氰酸酯、酸酐、羧酸，特别是醇，优选具有1-6个碳原子的醇，例如甲醇和异丁醇。为了进行接枝，聚合物中的马来酸酐单体或马来酸酐单元与反应物反应，特别是被醇酯化。马来酸酐基团优选仅部分地反应或酯化，特别是小于70％的马来酸酐基团反应或酯化。优选马来酸酐基团不反应并且继续以酸酐基团存在。在优选的实施方式中，马来酸酐基团也可以部分水解的形式存在。马来酸酐基团完全反应会导致得到的焊接连接的强度减小。
特别有利的是，基于共聚物，共聚物的马来酸酐含量大于或等于0.1重量％，特别是大于或等于0.5重量％，优选大于或等于4重量％，特别优选大于或等于8重量％。有利地，基于共聚物，共聚物的马来酸酐含量为0.1-50重量％，特别是0.5-40重量％，优选4-30重量％，特别优选8-26重量％。具有相应的马来酸酐含量的共聚物显示出特别好的焊接连接强度。
而且，共聚物的优选的玻璃化转变温度Tg(通过DSC以10K/min的加热速率在氮气中测定，特别是按照DIN EN ISO 11357-1:2010-3和DIN EN ISO 11357-2:2014-07测定)为大于30℃，特别是大于80℃，特别优选大于100℃。具有相应的玻璃化转变温度的共聚物特别地改善焊接连接在高温下的机械性能。
有利地，共聚物的重均分子量Mw大于或等于5000g/mol，特别是大于或等于50000g/mol，优选大于或等于100000g/mol。优选地，共聚物的重均分子量Mw为5000-2000000g/mol，特别是50000-1000000g/mol，优选100000-500000g/mol。具有相应的重均分子量的共聚物对获得的连接的脆性和强度具有积极影响。可以通过GPC相对于聚苯乙烯标准物测定重均分子量。
除了共聚物之外，底漆还可优选包含至少一种另外的聚合物。至少一种另外的聚合物或共聚物优选与待焊接的两种塑料材料中的至少一种相容并且与底漆共聚物相容。底漆特别优选包含至少一种聚酰胺聚合物和/或聚(甲基)丙烯酸酯聚合物，特别是聚(甲基丙烯酸甲酯)聚合物，优选在每种情况下含有上面详细说明的那些中的一种。最优选地，底漆包含至少一种聚(甲基丙烯酸甲酯)聚合物。在底漆中采用额外的聚合物和根据本发明的共聚物导致对强度产生进一步的改善。
优选地，用作相容的另外的聚合物的聚合物与待结合的两种塑料材料之间，特别是也与上面提及的根据本发明的第一聚合物之间的汉森参数(Hansen parameter)的加权的距离的平方(Ra)2，小于22MPa，特别是小于17MPa，优选小于15MPa，特别优选小于12MPa。
汉森参数的加权的距离的平方(Ra)2是根据下式测定的：
(Ra)2＝4(ΔδD)2+(ΔδP)2+(ΔδH)2
在该式中，δD是分散力的汉森参数，δP是极性的汉森参数，并且δH是氢桥键的汉森参数。在每种情况下，ΔδD、ΔδP和ΔδH表示与被比较的塑料材料或聚合物之间的这些汉森参数的差，例如ΔδD＝聚合物1与聚合物2的(δD1-δD2)。相关的塑料材料或聚合物的各个汉森参数δD、δP和δH的值是根据“Hansen Solubility Parameters:A User’s Handbook”byCharles M.Hansen(second edition；Taylor&Francis Group；2007；ISBN-10 0-8493-7248-8)”一书测定的。各聚合物的许多值已经可以从该资料中找到。根据该书中描述的方法，可以优选采用程序HSPIP(第4版4.1.07)从附随的数据库获得汉森参数，或者，如果这是不可得的，那么可以采用程序的内装的“DIY”功能，优选采用附随的神经式网络(neuralnetwork)测定，如“帮助”部分所述。HSPIP程序可得自Steven Abbott TCNF Ltd公司。
优选地，底漆中的至少一种聚(甲基)丙烯酸酯聚合物，特别是聚(甲基丙烯酸甲酯)聚合物的重均摩尔质量(重均分子量)大于50000g/mol，特别是大于100000g/mol。优选地，底漆中的聚(甲基)丙烯酸酯聚合物，特别是聚(甲基丙烯酸甲酯)聚合物的重均摩尔质量(重均分子量)小于2000000g/mol，特别是小于1000000g/mol，优选小于500000g/mol。底漆中的特别优选的聚(甲基)丙烯酸酯聚合物，特别是聚(甲基丙烯酸甲酯)聚合物的重均摩尔质量(重均分子量)为50000g/mol至250000g/mol。
在每种情况下，基于底漆的总重量，底漆中的另外的聚合物的含量，特别是聚(甲基丙烯酸甲酯)聚合物的含量优选为1-40重量％，特别是5-30重量％，特别优选10-20重量％。在每种情况下，基于底漆(底漆不含溶剂并且不含填料)的总聚合物含量，底漆中的另外的聚合物的含量，特别是聚(甲基丙烯酸甲酯)聚合物的含量，优选为5-70重量％，特别是20-60重量％，特别优选30-50重量％。
除了共聚物和所述另外的聚合物之外，底漆还可以包含溶剂，特别是有机溶剂。在每种情况下，基于所述底漆的总重量，优选地，底漆的溶剂含量为10-90重量％，特别是50-85重量％，特别优选60-80重量％。
所有的常规溶剂，例如水，醇，酮例如甲基异丁基酮(MIBK)或环己酮(CH)，醚例如乙醚或四氢呋喃(THF)，酯例如乙酸乙酯，或碳酸酯例如碳酸二甲酯或碳酸二丙酯或它们的混合物是合适的溶剂。
在优选的实施方式中，底漆包含有机溶剂。特别优选的溶剂是在20℃蒸气压为1-600hPa，特别是2-200hPa，特别优选5-20hPa的溶剂。在这种情况下，已经发现，具于相应的蒸气压的溶剂特别有利于在蒸发时将底漆层中的气泡形成最小化或者防止气泡形成。特别优选底漆包含选自四氢呋喃、甲基异丁基酮、环己酮及它们的混合物的溶剂，特别优选底漆包含四氢呋喃或甲基异丁基酮和环己酮的混合物。如果将甲基异丁基酮和环己酮的混合物用作溶剂，在每种情况下，基于总溶剂混合物，所述混合物优选包含10-50重量％，特别是20-35重量％的环己酮。
如果采用有机溶剂，在每种情况下基于底漆的总重量，底漆的总聚合物含量优选为10-90重量％，特别是15-50重量％，特别优选20-40重量％。总聚合物含量相应于底漆中采用的所有聚合物的含量，特别是根据本发明的共聚物和上述的另外的聚合物。
在另外的优选的实施方式中，底漆以含水分散体或乳液的形式存在。在这种情况下，根据本发明的共聚物和另外的聚合物(如果存在的话)在水中乳化或分散在水中。在这种情况下，在每种情况下基于底漆的总重量，底漆的总聚合物含量优选为5-90重量％，特别是10-70重量％，特别优选20-55重量％。对于含水分散体/乳液，有利的是，聚合物组分基本上仅由根据本发明的共聚物和任选存在的上面提及的另外的聚合物构成，特别是仅由根据本发明的共聚物构成。根据本发明，术语“基本上”理解为是指共聚物组分包含大于95重量％，优选大于97重量％，最特别优选大于99重量％的根据本发明的共聚物和任选存在的上面提及的另外的聚合物，特别是仅由根据本发明的共聚物构成。
除了根据本发明的共聚物、上面提及的另外的聚合物、和溶剂之外，底漆还可以包含另外的组分例如填料、(荧光)染料和颜料、流变助剂、消泡剂、润湿剂、稳定剂或增塑剂。但是，除了染料和颜料之外，底漆优选基本上不含另外的组分，特别是基本上不含任何其它组分。根据本发明，术语“基本上不含”指的是底漆包含小于5重量％，优选小于1重量％，最特别优选小于0.1重量％的相关物质，特别是不包含相关物质。
在根据本发明的焊接聚酰胺塑料和聚(甲基)丙烯酸酯塑料的方法中，采用底漆，底漆包含至少一种由至少一种苯乙烯或苯乙烯衍生物与至少一种马来酸酐或马来酸酐衍生物合成的共聚物。
在该方法中，在每种情况下，底漆用作通过熔融来焊接两种塑料的助剂，两种塑料是聚酰胺和聚(甲基)丙烯酸酯。所用包含根据本发明的共聚物的底漆使得可以在两个结合配件之间产生相容性，从而可以在两种塑料材料之间产生稳定和持久的整体结合连接。
可以采用各种方法将底漆施加至一个结合配件或两个结合配件的表面。因此，例如，可以采用计量装置，采用针和计量机器人，通过注塑，通过挤出，通过膜涂，通过作为热熔体施加，通过喷射，通过铺展，或者通过浸渍来施加所述底漆。
当施加底漆时，可以将所述底漆施加至待焊接基板的仅一个表面或施加至待焊接基板的两个表面。优选将底漆仅施加至一个表面，特别是聚酰胺表面。在采用膜焊接的情况下，将膜置于基板之间。
在底漆包含溶剂的情况下，在施加至一个或两个表面之后，优选使底漆干燥直至溶剂已经蒸发到获得不粘的、尺寸稳定的底漆层的程度。特别地，仅在几秒之后底漆就可焊接，并且可焊接的状态持续长达几周的时间。在施加之后，优选使底漆干燥至少一小时，优选至少12小时。
优选施加至待焊接基板的一个或两个表面，使得底漆的层厚度为1μm至5000μm，特别是10-3000μm，优选50-1000μm，特别优选100-500μm。如果底漆中包含溶剂，层厚度指的是已经将溶剂干燥掉的底漆。
在已经将底漆施加到待焊接基板的一个或两个表面之后，并且任选地在已经使底漆干燥之后，可以采用常规的焊接方法将待焊接的基板互相连接。通常通过将结合配件在结合面局部塑化(plasticization)，并且在压力下结合来进行塑料材料的焊接。应该选择工艺参数，使得熔体的显著的经挤压的流动导致结合配件在结合面具有最佳连接。可以通过对流、接触加热、辐射或摩擦来进行加热。可以各种方式发生塑化的不同能量输入，并且已经得到焊接塑料材料的不同方法。合适的焊接方法有，例如：
·热气焊接[HG]
对流加热，采用热气流，通常是空气，两阶段法
·热板焊接[HP]
接触加热，两阶段法
·超声焊接[US]
通过摩擦来加热，超声范围的横波导致在边界层加热，一阶段法
·高频焊接[HF]
通过内部摩擦来加热，极性分子按照高频磁场取向，一阶段，仅用于极性塑料材料和膜
·摩擦焊接[FRW]：线性的；轨道的；旋转；角
通过摩擦来加热，一阶段法
·激光焊接[LW]：轮廓的，同步，半同步，掩模
通过辐射来加热，相干辐射，激光传输焊接，通常是一阶段(可以是两阶段)
·红外焊接[IR]
通过辐射来加热，非相干辐射，两阶段
任选地，也可以将上面列举的焊接方法组合，例如，红外焊接和摩擦焊接。特别优选采用选自热板焊接、热接触或热脉冲焊接、温气或热气焊接、微波或感应焊接的焊接方法，将聚酰胺塑料与聚(甲基)丙烯酸酯塑料焊接。激光碰撞或激光辐照焊接、红外焊接、超声焊接和它们的组合，特别是选自红外焊接、超声焊接、摩擦焊接和它们的组合。
包含以下步骤的采用底漆将两种塑料材料整体结合的方法是特别优选的：
·提供包含第一结合区的第一塑料材料，
·提供包含第二结合区的第二塑料材料，
·预热第一结合区，
·将底漆施加至预热的第一结合区，特别是在不含溶剂的底漆的情况下，
·使带有底漆的第一结合区与第二结合区接触，
·将第一结合区与第二结合区整体连接，特别是通过采用常规的塑料材料焊接方法，例如红外焊接、热板焊接、热气焊接、摩擦焊接、超声焊接。
通常，DIN 1910-3:1977-09可用于焊接塑料材料。因此，在该上下文中可以理解采用热和/或压力将热塑性材料整体结合。例如基于接触加热(采用固体的焊接)，对流加热(采用热气的焊接)，辐射加热(采用光束的焊接)，和通过摩擦的加热(通过移动的焊接)，以及通过电力的焊接，可以进行加热。
在有利的方案中，采用经选择并适合方法的底漆，使得在低于底漆中的聚合物的分解温度的温度下，将底漆施加至经加热的和/或热的结合区，不会对底漆的内部化学交联产生任何影响。
将第一塑料材料的第一结合区预热是有利的。可以将本领域技术人员已知的适于所述目的的助剂和技术用于预热。特别地，采用热气或等离子体适于预热。通过辐射来预热，特别是通过红外辐射或激光辐射来预热也是可以的。加热元件或被加热的工具也可用于预热第一结合区。最后，在烘箱中或在经加热的室(heated room)中预热也是可以的。预热整个塑料材料以及由此也预热所述结合区是可以的。但是，作为替代或者额外地，也可以仅预热结合区本身。
在有利的方案中，在预热期间，加热装置与塑料材料之间的间距，特别是加热装置与待预热的第一结合区之间的间距，特别是加热装置的发射热量的区域或加热装置的发射热量的区域或加热装置的待被预热的有效表面或加热装置的与第一结合区相对的区域与待预热的第一结合区之间的间距是0.5mm至100mm，优选1mm至60mm。作为替代，也可以通过特别地使第一结合区与加热装置的加热元件接触和/或在接触的同时来进行加热。
为第一结合配件选择塑料材料并且根据第一塑料材料调整方法参数，从而当预热时，第一结合区熔融，并且通过预热，在第一结合区产生熔体层，这是另一个优点。在特别优选的实施方式中，熔体层的厚度优选为0.05mm至6mm，特别优选0.1mm至5mm。这种熔体层可以得到分子的更好的粘合和/或扩散和/或相互作用，以及特定的流动，也可以导致改善的连接层。如果第一塑料材料的边界层是熔融状态的，可以发生直至与底漆化学连接的相互作用。熔体层可以特别地取决于组分几何学和相关组分设计。优选地，调整和/或选择方法参数，从而不发生组分的变形。采用合适的手段和/或方法步骤，优选将结合区与待施加的底漆之间的温差均衡。在这种情况下，特别是可以预热底漆，以便减少优选的热塑性底漆与第一结合区之间的温差。这可以例如抵消第一结合区在方法步骤之间的快速冷却。
任选地，将第一结合区预处理，优选在预热第一结合区的步骤之前进行。作为替代或额外地，也可以将第二结合区预处理。例如采用溶剂或例如碱性塑料清洁剂进行清洁可以是可能的预处理。也可以采用机械预处理，特别是通过刮擦、抛光、刷洗或辐射。可能的化学预处理特别是酸性清洗或采用反应性气体。而且，采用热、化学和/或物理预处理可以证明是有利的，特别是通过气体火焰或等离子弧。作为替代或额外地，可以通过电晕放电进行电预处理，在此期间，使第一结合区和/或第二结合区接受电的电晕放电，从而在相应的表面得到极性分子。另外的选择是等离子处理，优选采用等离子喷嘴，来预处理结合区，特别是为了活化和/或清洁相应的表面。但是，通过等离子体来涂布也可以证明是有利的。另外的选择是燃烧结合区，从而在合适的塑料材料中增加表面张力。另外类型的预处理是采用紫外线、电子束、放射线或通过激光进行辐射。最后，也可以涂布的方式，特别是通过涂抹或采用助粘剂来进行预处理。在预热之前，也可以将第一塑料材料或第一塑料材料的结合区域预处理更长的时间。因此，可以例如在制备第一塑料材料的方法中已经进行过预处理，以便能够在根据本发明的方法中进一步加工预处理的塑料材料。
可以各种方式施加底漆。例如，特别是在工业领域，可以采用自动施加工具，特别是通过计量机器人来施加。在这种情况下，所述机器人可以装配有针和/或高度传感器，以便能够进行复杂的计量方法。也可以通过注塑来施加底漆，其中底漆在注塑机器中塑化并且在压力下注射到模具中，所述模具包含包括第一结合区的第一塑料材料。作为替代，可以采用膜施加，首先通过薄膜吹塑或平膜挤出来由底漆制备膜。然后，例如通过切割或冲压方法，可以将膜切成任何期望的形状，并且，在所提及的预热之后，在另外的步骤中，可以将膜施加到第一结合区。在这种情况下，已经发现采用厚度为1μm-5000μm的膜/板是有利的。另外可以想到的可能的施加方式有挤出焊接，在此期间，底漆以焊丝的形式存在，或者在挤出机中熔融并且可以熔融形式施加至第一结合区。也可以焊丝的形式提供底漆，以便使通过热气焊接来施加成为可能。另外的选择是通过喷射的方法施加底漆。在注塑期间施加的情况下，对注塑工具进行预处理和/或预热和/或局部不同的温度控制也是可以的。当然，本领域技术人员已知的并且适于具体用途的其他类型的施加也是可以的。
进一步加热第一结合区或在施加底漆的同时加热第一结合区，特别地为了防止第一结合区的温度在预热与施加底漆之间下降，是另外的优点。可以通过上述预热方法步骤进行所述加热，为了简单起见，在施加期间可以继续加热。作为替代或额外地，额外的加热，特别是通过另外的方法步骤进行额外的加热是可能的。因此，可以证明有利的是，例如，在施加底漆期间同时加热第一结合区，例如通过将第一结合区同时暴露于辐射、强制对流和接触加热，以便防止第一结合区的温度在预热之后下降。
在有利的实施方式中，施加底漆，从而厚度为1μm至5mm，优选10μm至3mm的连接层置于第一结合区上。在这种情况下，连接层的厚度理解为第一结合区上的连接层的材料厚度。
另外的优点是在第一结合区和计量装置相对于彼此移动的同时，通过计量装置将底漆施加到第一结合区，在施加底漆之前，在第一结合区和加热装置相对于彼此移动的同时，通过加热装置预热向其施加底漆的第一结合区，当第一结合区处于预热状态时，通过计量装置施加底漆。
在这种情况下，已经发现特别有利的是，在预热期间，加热装置以10mm/min至100mm/min，优选10mm/min至30mm/min的速度移动通过第一结合区。
加热装置位于计量装置前面可以是进一步有利的，优选具有确定和恒定的间隔。特别地，有利的是以下述方式实施所述方法：在计量装置和第一结合区以10mm/min至100mm/min，优选10mm/min至30mm/min的速度相对于彼此移动的同时，通过计量装置将底漆施加至第一结合区，在施加底漆之前，在加热装置和第一结合区相对于彼此移动的同时，通过加热装置预热向其施加底漆的所述结合区，加热装置优选在同一时间位于计量装置的前面，或施加底漆的计量装置的喷嘴具有0.1-10秒的时滞。
在这种情况下，已经发现特别有利的是，采用由计量装置和加热装置组成的涂布单元。在这种情况下，涂布单元可以特别理解为在加热装置与计量装置之间提供刚性连接的单元，使得在相对移动的过程中，加热装置优选以固定和恒定的间距位于计量装置前面，以便确保在施加底漆之前即刻将第一结合区预热。当然，可以想象的是，在这种情况下间距可调节，或者在对流预热的情况下，调节介质的容量流量和/或喷嘴直径，特别是通过合适的机械的、机电的或气动控制的调节器调节。
与之相对地，涂布单元也可理解为处于两个完全独立或分离的模块形式的加热装置和计量装置，但是，所述加热装置和计量装置相对于塑料材料进行相同或基本相同的相对移动，以便确保在施加底漆之前即刻施加底漆的位置被预热。
在有利的方案中，尽管加热装置和计量装置相对于塑料材料进行具有基本相同的基础方向的基本相同的主要的相对移动，除了相对于塑料材料的所述主要的相对移动之外，两种所提及的装置中的至少一种经历额外的相对移动。因此，例如，除了主要的相对移动之外，加热装置和/或计量装置可以进行一种或多种次要的相对移动，在此期间，例如，也可以涂布底漆。例如，特别是加热装置和/或计量装置可以进行或经历环绕主要的相对移动或者围绕主要的相对移动蜿蜒曲折进行的次要的相对移动。
在这种情况下，一方面塑料材料可以移动，或加热装置和计量装置或这两种装置一起作为涂布单元可以移动。在这种情况下，一方面加热装置和计量装置或这两种装置一起作为涂布单元，另一方面塑料材料，在每种情况下可以是静止的或它们的移动部分在不同方向移动。
在有利的方案中，以10mm/min至100m/min，优选10mm/min至30m/min的速度进行主要的相对移动，从而例如，特别是也归因于加热装置的合适的设计，塑料材料在加热装置的加热表面中的停留时间尽可能地短，特别是为1-60秒。这可以理解为影响第一塑料材料的第一结合区的温度的加热装置周围的区域或空间，所述影响温度是在增加温度的意义上的，即，预热。因此，例如可以避免过度加热和损坏塑料材料或塑料材料的降解。
而且，可以证明有利的是，特别是为了将计量装置和/或加热装置连接至现有的生产线或连接至现有的生产线中，使加热装置装配有总线接口特别是PROFIBUS或实时以太网接口。
在已经施加所述底漆之后，使第二结合区与底漆层接触。在这种情况下，可以证明有利的是，将两种塑料材料固定在一起，特别是通过本领域技术人员已知的夹紧装置或类似的固定助剂。
当然，在使第二结合区与底漆层接触的步骤之前，可以任选地预处理第二结合区。在这种情况下，特别是所有上述的预处理技术都是可以想象的。也可以想象的是，在接触之前，将第二塑料材料或第二塑料材料的结合区预处理更长的时间。因此，可以想象的是，例如，在制备第二塑料材料的方法期间已经进行预处理，以便能够在根据本发明的方法中进一步加工预处理的塑料材料。第二塑料材料的预处理也可以包括将底漆施加至第二结合区。在这种情况下，优选在施加底漆之前也可以预热第二结合区。这里，以上实施方式也是优选的。
如上所述，使第二结合区和底漆接触，然后进行结合方法，其中通过供热将经处理和/或经涂布的结合配件塑化并且整体相互连接，优选在压力的作用下进行。可以通过以下方式采用供热来进行第二结合区与底漆之间的该整体连接，通过热传导例如通过热板焊接和/或热接触焊接和/或热脉冲焊接；通过摩擦，特别是超声、摩擦或高频焊接；微波或感应焊接；通过对流，例如温气或热气焊接；通过辐射，例如红外、激光碰撞或激光辐照焊接，或通过上述技术中的两种或更多种的组合。
本发明还涉及根据本发明的方法制备的制品或产品。
而且，本发明涉及根据本发明的底漆用于焊接聚酰胺塑料和聚(甲基)丙烯酸酯塑料的用途。
实施例
所用的材料和缩写：
PA＝聚酰胺
PA 6＝聚己内酰胺，Durethan BKV30
PA 6.6＝聚-(N,N'-六亚甲基己二酰己二胺)；Ultramid A3K
PMMA＝聚甲基丙烯酸甲酯
PMMA 1＝Polycasa G87E
PMMA 2＝Plexiglas 8N
MAH＝马来酸酐
过氧化物＝Luperox A75(75重量％的过氧化苯甲酰，25重量％的水)
THF＝四氢呋喃
MIBK＝甲基异丁基酮
CH＝环己酮
共聚物SM1＝具有15重量％的MAH和Mw为170000g/mol的苯乙烯-马来酸酐共聚物
共聚物SM2＝具有8重量％的MAH和Mw为250000g/mol的苯乙烯-马来酸酐共聚物
共聚物SM3＝具有26重量％的MAH和Mw为180000g/mol的苯乙烯-马来酸酐共聚物
共聚物SM4＝苯乙烯-马来酸酐共聚物；Mw为180000g/mol并且用异丁基/甲基部分酯化
IR：红外焊接；IR-FR：红外/摩擦焊接；US：超声焊接
苯乙烯-马来酸酐-甲基丙烯酸甲酯共聚物SMA 5和6的制备
根据上表，通过本体(bulk)自由基聚合来由苯乙烯、甲基丙烯酸甲酯和马来酸酐合成共聚物。将所有起始材料和引发剂均称量至1升的2颈烧瓶中，并且在油浴中非常缓慢地加热至油浴温度为95℃，同时通过磁力搅拌子剧烈搅拌。在已经形成固体化合物之后，将所述化合物加热至140℃并持续4小时。将反应产物溶解在100ml THF中，在冷却至20℃之后，使其在300ml甲醇中沉淀。在过滤之后，采用布氏漏斗，在真空下从得到的共聚物中除去残留的溶剂。得到无色固体。
底漆1-10的制备：
为了制备底漆，通过机械搅拌将聚合物组分溶解在溶剂中，并且在25℃脱气。在下表中可以发现底漆的组成，单位为g。
底漆11-13的制备：
根据上表，通过在水中乳液聚合，由苯乙烯、甲基丙烯酸甲酯和马来酸酐合成共聚物。可以从下表中发现单体彼此之间的各个比例。
制备底漆11和12，从而得到具有52重量％的水含量和0.5重量％的的表面活性剂Disponil SDS G的乳液。对于底漆13，去除水，并且将得到的共聚物溶解在75重量％的THF中。
可以制备共聚物和/或底漆的分散体，所述分散体在室温下几周都没有呈现出任何沉淀。
总体测试的实施：
在室温下，向待焊接的PA塑料材料的下半部分(在下表中相应地标出其偏差)表面(130mm x 3mm)施加底漆。然后，在室温下将底漆干燥以除去溶剂，并持续24小时。在干燥之后，底漆的厚度为约0.2mm。然后，将几何形状为130mm x 68mm x 3mm的预先干燥的塑料组分头尾衔接地焊接到130mm x 3mm表面。在室温下，以5mm/s的牵引速度测定拉伸强度。在各种情况下，下面的表格显示，对于底漆与塑料材料的组合和所用的焊接方法，焊接的测试样品能够实现的拉伸强度(单位为MPa)：
IR和IR-FR焊接：
超声焊接:
结果显示，采用底漆焊接的样品呈现出优异的拉伸强度。还可以看出，包含环己酮和甲基异丁基酮的混合物作为溶剂的底漆在蒸发溶剂之后没有任何气泡。但是，蒸发溶剂所需的时间随着环己酮的增加而增加。
焊接的样品的老化测试：
对于老化测试，用底漆7涂布PA塑料基板，如上面所实施的。然后，在约280℃的温度，以对于PMMA为15秒的加热时间和对于PA 6.6为45秒的加热时间，通过手工热板焊接将塑料材料PA 6.6和PMMA 2连接。然后对于老化测试，将样品在一个温度下储存指定的时间，然后在室温下进一步储存24小时，在室温下进行拉伸强度测试。结果如下：
结果显示了焊接样品的优异的老化稳定性。

Claims (13)

1.采用底漆焊接聚酰胺塑料和聚(甲基)丙烯酸酯塑料的方法，所述聚(甲基)丙烯酸酯特别是聚甲基丙烯酸甲酯，其中所述底漆包含至少一种由至少一种苯乙烯或苯乙烯衍生物与至少一种马来酸酐或马来酸酐衍生物合成的共聚物。
2.根据权利要求1所述的焊接方法，其特征在于，所述聚酰胺塑料选自聚酰胺6、聚酰胺6.6、聚酰胺6.10、聚酰胺6.12、聚酰胺10.10、聚酰胺11、聚酰胺12、聚酰胺10.12、聚邻苯二甲酰胺、光学透明的聚酰胺或基于所述聚酰胺的混合物。
3.根据权利要求1或2所述的焊接方法，其特征在于，所述聚(甲基)丙烯酸酯塑料包含50-100重量％，特别是70-100重量％的甲基丙烯酸甲酯，和/或所述聚甲基丙烯酸甲酯塑料的摩尔质量(重均分子量)大于50000g/mol，和/或所述聚(甲基)丙烯酸酯塑料是聚甲基丙烯酸甲酯塑料。
4.根据权利要求1-3中任一项所述的焊接方法，其特征在于，在所述至少一种共聚物中，苯乙烯与马来酸酐的摩尔比为1:0.01-1:2，优选1:0.05-1:1，特别优选1:0.1-1:0.3。
5.根据权利要求1-4中任一项所述的焊接方法，其特征在于，所述至少一种共聚物还含有通过聚合并入的另外的单体，优选选自丙烯酸酯和甲基丙烯酸酯的单体。
6.根据权利要求1-5中任一项所述的焊接方法，其特征在于，基于所述至少一种共聚物，所述至少一种共聚物的马来酸酐含量为0.1-50重量％，特别是0.5-40重量％，优选4-30重量％，特别优选8-26重量％。
7.根据权利要求1-6中任一项所述的焊接方法，其特征在于，所述底漆中的至少一种共聚物的玻璃化转变温度Tg大于30℃，特别是大于80℃，特别优选大于100℃.
8.根据权利要求1-7中任一项所述的焊接方法，其特征在于，所述至少一种共聚物的重均分子量Mw为5000-2000000g/mol，特别是50000-1000000g/mol，优选100000-500000g/mol。
9.根据权利要求1-8中任一项所述的焊接方法，其特征在于，除了所述共聚物之外，所述底漆还包含至少一种另外的聚合物，所述另外的聚合物与所述两种待焊接的塑料材料中的至少一种相容，所述另外的聚合物优选为至少一种聚酰胺聚合物和/或至少一种聚(甲基)丙烯酸酯聚合物，所述聚(甲基)丙烯酸酯特别是聚甲基丙烯酸甲酯，所述另外的聚合物优选为聚甲基丙烯酸甲酯聚合物。
10.根据权利要求1-9中任一项所述的焊接方法，其特征在于，所述底漆包含至少一种溶剂，特别是至少一种有机溶剂，在每种情况下，基于所述底漆的总重量，所述底漆的溶剂含量优选为10-90重量％，特别是50-85重量％，特别优选60-80重量％。
11.根据权利要求10所述的焊接方法，其特征在于，所述至少一种溶剂在20℃的蒸气压为1-600hPa，特别是2-200hPa，特别优选5-20hPa，优选所述溶剂选自四氢呋喃、甲基异丁基酮MIBK、环己酮及它们的混合物。
12.根据权利要求1-11中任一项所述的焊接方法制备的制品。
13.底漆在根据权利要求1-11中任一项所述的焊接聚酰胺塑料和聚甲基丙烯酸甲酯塑料的方法中的应用。
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