CN108136682A - 焊接两种不同的聚烯烃塑料的方法 - Google Patents

焊接两种不同的聚烯烃塑料的方法 Download PDF

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Publication number
CN108136682A
CN108136682A CN201680060610.8A CN201680060610A CN108136682A CN 108136682 A CN108136682 A CN 108136682A CN 201680060610 A CN201680060610 A CN 201680060610A CN 108136682 A CN108136682 A CN 108136682A
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China
Prior art keywords
priming paint
polymer
maleic anhydride
grafting
polyolefin
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CN201680060610.8A
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English (en)
Inventor
P·沃尔特
N·费里德里克
L·冈萨雷斯
H·吕岑
T·黑蒂希
D·卡斯珀
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of CN108136682A publication Critical patent/CN108136682A/zh
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B29C66/712—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined the composition of one of the parts to be joined being different from the composition of the other part
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

本发明涉及采用底漆焊接两种不同的聚烯烃塑料的方法，所述底漆包含至少一种马来酸酐接枝的聚烯烃聚合物。本发明还涉及相应的焊接产品。

Description

焊接两种不同的聚烯烃塑料的方法
本发明涉及采用底漆焊接两种不同的聚烯烃塑料材料的方法，其中所述底漆包含至少一种马来酸酐-接枝的聚烯烃聚合物。本发明还涉及以这种方式焊接的产品。
本领域已知各种将两种或更多种由塑料材料制成的基板相互连接的方法，塑料材料例如聚乙烯(PE)、聚丙烯酸酯或聚酰胺(PA)。这涉及机械连接选择(例如锁住或螺接)或粘结方法。作为替代，也可以将塑料材料焊接在一起。焊接是对于通常是相同类型的塑料材料(例如PE与PE或PA与PA)的不可拆卸的、材料的物理连接的结合方法。相同类型的热塑性材料是在分子结构、熔点、熔融粘度和热膨胀系数方面相差不大并且原则上在一定程度上可以混合在一起的那些聚合物。相同类型的塑料材料是具有相同的聚合物分子结构的塑料材料或是相同的塑料材料。
已知许多方法可以将两种或更多种相同类型的塑料材料焊接在一起。在这种情况下，可以采用多种焊接方法，例如红外焊接，红外/振动焊接或超声焊接。这些焊接相同类型的塑料材料的方法基于各种塑料材料在焊接区的区域中熔化，并且在该区域物质彼此之间整体结合并且以摩擦的方式相互连接。
只要准备将相同类型的塑料材料相互连接，那么这些焊接方法是有效的。但是，如果打算将不同类型的或彼此不相容的两种塑料材料焊接在一起，例如由聚酰胺与聚(甲基)丙烯酸酯制成的塑料材料，不可能在两个基板之间产生具有高的机械强度的持久连接。但是，即使在相似的塑料材料(例如聚乙烯和聚丙烯)的情况下，焊接通常在焊缝中产生不充分的强度。
因此，迄今为止，只能通过机械连接或者粘结方法将不同的塑料材料互相连接。机械连接的缺点是复杂的附件、在某些点的材料应变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，粘结低能表面通常需要对结合部件进行复杂的预处理。而且，因为外部大气条件，粘结连接也不确定地不稳定。提供清洁的粘结经常也是复杂和费时的。因此，通过焊接塑料材料的方法进行连接代表最清洁、最快速和最简单的解决办法。
因此，本发明的目的是发现焊接两种不同的聚烯烃塑料材料的简单方法，所述方法相对于现有技术改善得到的连接的强度。因此，由于焊接，所述塑料材料之间的连接应该是持久和尽可能稳定的。
令人惊奇地，发现通过采用底漆焊接两种不同的聚烯烃塑料材料的方法实现了该目的，其中所述底漆包含至少一种马来酸酐-接枝的聚烯烃聚合物。
当焊接两种不同的聚烯烃塑料材料时，通过采用包含至少一种相应的共聚物的底漆，可以在聚烯烃塑料材料之间实现特别稳定和耐老化的的连接。
采用根据本发明的底漆焊接的结合部件是两种不同的聚烯烃塑料材料。相同的聚烯烃塑料材料理解为是指它们的聚合物结构或填料类型没有不同的两种聚烯烃。合适的聚烯烃塑料材料特别是热塑性聚烯烃塑料材料。聚烯烃塑料材料基于聚烯烃类聚合物(polyolefinic polymers)，例如α-烯烃的均聚物和共聚物。聚烯烃类聚合物可选自基于乙烯、丙烯和/或丁烯的聚-α-烯烃均聚物，特别是乙烯均聚物或丙烯均聚物，和基于乙烯、丙烯、1-丁烯、1-己烯和1-辛烯的聚-α-烯烃共聚物，特别是乙烯/α-烯烃共聚物和丙烯/α-烯烃共聚物，优选具有1-丁烯、1-己烯、1-辛烯或它们的组合的乙烯或丙烯的共聚物。聚烯烃塑料材料特别是选自聚乙烯塑料材料(特别是高-密度/HD聚乙烯、中等-密度/MD聚乙烯、低-密度/LD聚乙烯、超-高-分子量/UHMW聚乙烯和线性低-密度/LLD-聚乙烯)和聚丙烯塑料材料。特别优选地，第一结合部件是聚乙烯-塑料材料，特别是HD聚乙烯、MD聚乙烯、LD聚乙烯、UHMW聚乙烯或LLD聚乙烯塑料材料，优选HD聚乙烯、MD聚乙烯或LD聚乙烯塑料材料，并且第二结合部件是聚丙烯塑料材料。因此，优选地，采用根据本发明的底漆将聚乙烯塑料材料与聚丙烯塑料材料焊接。聚乙烯塑料材料特别优选是基于乙烯的；特别地，聚乙烯聚合物是由大于50重量％，特别是大于70重量％，优选大于90重量％，特别优选100％的乙烯制备的。
优选地，聚烯烃聚合物，特别是聚乙烯聚合物和/或聚丙烯聚合物的重均摩尔质量(重均Mw)大于10,000g/mol，特别是大于20,000g/mol，优选大于50,000g/mol。优选地，聚烯烃聚合物，特别是聚乙烯聚合物和/或聚丙烯聚合物的重均摩尔质量(重均Mw)大于2,000,000g/mol，特别是大于1,000,000g/mol，优选大于500,000g/mol。特别优选的聚烯烃聚合物，特别是聚乙烯聚合物和/或聚丙烯聚合物的重均摩尔质量(重均Mw)为50,000g/mol至250,000g/mol。特别优选的聚乙烯聚合物的重均摩尔质量(重均Mw)为50,000g/mol至1,000,000g/mol，特别是200,000g/mol至500,000g/mol。其他优选的聚乙烯聚合物(UHMW PE聚合物)的重均摩尔质量大于2,000,000g/mol，特别是4,000,000g/mol至6,000,000g/mol。
聚烯烃塑料材料，特别是聚乙烯塑料材料和/或聚丙烯塑料材料，还可以包含另外的组分，例如填料，例如玻璃纤维，颜料，染料，流变助剂，脱模助剂(demolding aids)或稳定剂。在每种情况下，基于聚烯烃塑料材料(总聚烯烃塑料材料，不含填料)的聚合物部分，聚烯烃塑料材料，特别是聚乙烯塑料材料和/或聚丙烯塑料材料，特别优选以大于80重量％，特别是大于90重量％，优选大于98重量％的量包含特定的聚烯烃聚合物，特别是特定的聚乙烯聚合物和/或聚丙烯聚合物。在每种情况下，基于总聚烯烃塑料材料(含有填料)，聚烯烃塑料材料优选以大于50重量％，特别是大于70重量％，优选大于90重量％，更优选大于95重量％，特别优选大于98重量％的量包含特定的聚烯烃聚合物，特别是聚乙烯和/或聚丙烯。
对本发明很重要的另一方面是至少一种底漆，优选刚好一种底漆的用途。底漆包含至少一种马来酸酐-接枝的聚烯烃聚合物。
底漆由焊接助剂组成，在结合区的区域内，焊接助剂优选作为预处理层施加至基板的待焊接的至少一个表面。底漆不应理解为粘合剂、清洁剂或类似物，而是底漆是焊接助剂，其使得结合部件在结合区(或焊接区)彼此相容，从而当结合发生时，在结合区实现待焊接基板之间的整体结合和摩擦连接。
实验已经显示，通过采用包含根据本发明的聚合物的相应的底漆，在焊接的情况下，可以使待结合的塑料材料在接缝处相容，因此可以实现稳定和持久的连接。如果不使用相应的底漆，只能实现较低强度的焊接连接。优选地，结合的基板的拉伸强度大于12MPa，特别是大于15MPa。以50mm/s的拉伸速度并且根据实验中描述的实验技术来测定拉伸强度。
底漆包含至少一种马来酸酐-接枝的聚烯烃聚合物，其特别是选自马来酸酐-接枝的聚乙烯或马来酸酐-接枝的聚丙烯。可以用马来酸酐或马来酸酐衍生物，特别是马来酸酐将聚烯烃接枝。马来酸酐衍生物的一个实例是1,2,3,6-四氢邻苯二甲酸酐，其包含相关的5-元酸酐基团。底漆优选包含马来酸酐-接枝的聚烯烃的混合物。混合物可以包含两种或更多种，优选两种不同的马来酸酐-接枝的聚烯烃聚合物。本领域技术人员理解的是，不同的马来酸酐-接枝的聚烯烃聚合物是在分子结构方面不同的两种聚合物，例如在分子量或单体组成方面不同。底漆优选包含至少一种马来酸酐-接枝的聚乙烯和至少一种马来酸酐-接枝的聚丙烯的混合物。不同的马来酸酐-接枝的聚烯烃聚合物的比例，特别是马来酸酐-接枝的聚乙烯与马来酸酐-接枝的聚丙烯的比例为0.2:1-20:1，特别是0.5:1-10:1，优选1:1-5:1，特别优选1.5:1-3:1.
可以已知方式合成聚合物。聚烯烃聚合物也可以包含少量的非-α-烯烃单体，例如苯乙烯或丙烯酸酯。聚烯烃聚合物优选不是嵌段共聚物。特别地，聚烯烃包含小于10重量％，优选小于2重量％，更优选小于1重量％的选自苯乙烯和丙烯酸酯的单体，特别优选不含选自苯乙烯和丙烯酸酯的单体，特别是非-α-烯烃单体。可以在与聚合物类似的反应中使聚合物进一步接枝。用于接枝的特别优选的反应配体是醇、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。为了接枝，聚合物中的马来酸酐单体或马来酸酐单元可以与反应配体反应，特别是采用醇或采用胺。特别地，聚合物也可以与马来酸酐进一步接枝，以便增加马来酸酐的含量。特别是在聚烯烃混合物的情况下，特别是聚乙烯和聚丙烯，所述聚烯烃可以进一步接枝，特别是与胺，优选与二胺进一步接枝，以便相互连接。优选地，仅一部分马来酸酐基团反应，特别是小于90摩尔％，优选小于70摩尔％的马来酸酐基团反应。优选地，一部分马来酸酐基团与胺，特别是脂肪族胺，优选脂肪族二胺，例如六亚甲基二胺反应。根据本发明的聚合物的优选5-100摩尔％，特别是10-80摩尔％，优选20-70摩尔％的马来酸酐基团，特别是马来酸酐-接枝的聚烯烃聚合物的混合物的所述比例的马来酸酐基团，与胺反应。
在另外的优选实施方式中，马来酸酐基团不反应，并且继续作为酐存在。在优选的实施方式中，马来酸酐基团也可以部分水解。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。
基于聚烯烃聚合物或它们的混合物，聚合物，特别是聚烯烃聚合物的混合物，包含的马来酸酐含量不小于0.001重量％，特别是不小于0.01重量％，优选不小于0.02重量％，特别优选不小于0.05重量％是特别有利的。有利地，基于聚烯烃聚合物或它们的混合物，聚合物或混合物包含的马来酸酐含量为0.01-15重量％，特别是0.02-10重量％，优选0.5-5重量％。在另外的优选实施方式中，基于聚烯烃聚合物或它们的混合物，聚合物或混合物包含的马来酸酐含量为2-15重量％，特别是5-10重量％。聚烯烃聚合物的相应的马来酸酐含量具有特别好的焊接连接强度。
有利地，马来酸酐-接枝的聚烯烃聚合物的重均分子量Mw不小于5,000g/mol，特别是不小于50,000g/mol，优选不小于100,000g/mol。共聚物优选的重均分子量Mw为5,000-2,000,000g/mol，特别是50,000-1,000,000g/mol，优选100,000-500,000g/mol。具有相应的重均分子量的聚合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。
不同的马来酸酐-接枝的聚烯烃的混合物是特别优选的，特别是马来酸酐-接枝的聚乙烯和聚丙烯的混合物。当在底漆中采用相应的混合物时，在拉伸强度方面观察到特别好的结果。底漆优选以至少50重量％，特别是70重量％，优选90重量％，更优选95重量％，特别优选99重量％的量包含相应的混合物。
除了根据本发明的聚合物之外，底漆优选还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是与待焊接的两种塑料材料中的至少一种相容并且与底漆相容的聚烯烃聚合物。特别优选地，底漆包含至少一种不含马来酸酐基团的聚烯烃聚合物，特别是不含马来酸酐基团的聚乙烯和/或聚丙烯。在根据本发明的底漆中，与马来酸酐-接枝的聚烯烃聚合物一起采用额外的聚合物会导致强度的进一步改善。
作为相容的另外的聚合物，相对于待结合的一种塑料材料，特别是相对于待结合的两种塑料材料，特别是也相对于上面所提及的根据本发明的第一聚合物，优选采用汉森参数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的聚合物。
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。ΔδD、ΔδP和ΔδH分别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“HansenSolubility Parameters:A User’s Handbook”by CharlesM.Hansen(secondedition；Taylor&Francis Group；2007；ISBN-10 0-8493-7248-8)”一书测定的。各聚合物的许多数值已经可以采用该资源检索到。根据该书中描述的方法，优选采用程序HSPIP(第4版4.1.07)从所提供的数据库检索到汉森参数，或者，如果检索不到的话，那么采用程序中包含的“DIY”功能，优选采用所提供的神经式网络(neural network)检索，如“帮助”部分所述。HSPIP程序可得自Steven Abbott TCNF Ltd公司。
在每种情况下，基于底漆的总重量，另外的聚合物，特别是不含马来酸酐基团的聚烯烃聚合物在底漆中的含量优选为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(不含溶剂并且不含填料的底漆)的总聚合物部分，另外的聚合物，特别是不含马来酸酐基团的聚烯烃聚合物在底漆的聚合物含量中的含量优选为5-70重量％，特别是20-60重量％，特别优选30-50重量％。
在特别优选的实施方式中，底漆不包含任何不含马来酸酐基团的另外的聚乙烯聚合物和/或聚丙烯聚合物，特别是不包含不含马来酸酐基团的聚烯烃聚合物。
除了根据本发明的聚烯烃聚合物和另外的聚合物之外，底漆还可以包含溶剂，特别是有机溶剂。在每种情况下，基于底漆的总重量，底漆优选的溶剂含量为10-95重量％，特别是50-90重量％，特别优选70-85重量％。
合适的溶剂是所有的常见溶剂，例如水，醇例如乙醇，烷烃例如异辛烷，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，甲苯，二甲苯或它们的混合物。
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1-90重量％，特别是2-50重量％，特别优选5-15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聚烯烃聚合物和上述另外的聚合物。
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，根据本发明的聚烯烃聚合物和另外的聚合物(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20-70重量％，特别优选30-55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聚烯烃聚合物或它们的混合物和上面提及的另外的聚合物(如果存在的话)构成，特别是仅由根据本发明的聚合物或它们的混合物构成。根据本发明，术语“基本上”理解为是指聚合物组分包含大于95重量％，优选大于97重量％，最特别优选大于99重量％的根据本发明的聚烯烃聚合物上面提及的另外的聚合物(如果存在的话)，特别是仅由根据本发明的聚烯烃聚合物或它们的混合物构成。
在特别优选的实施方式中，底漆基本上不含溶剂。
除了根据本发明的聚烯烃聚合物，特别是马来酸酐-接枝的聚乙烯和聚丙烯的混合物，上面所提及的另外的聚合物和溶剂之外，底漆还可包含另外的组分，例如填料、(荧光)染料和颜料、消泡剂、流变助剂、润湿剂、稳定剂或增塑剂。特别是对于底漆基本上不含溶剂的情形，另外的组分的含量可以不超过70重量％，特别是不超过50重量％，优选不超过30重量％。但是，除了染料和颜料之外，底漆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％，非常特别优选小于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两种不同的聚烯烃塑料材料的方法中，采用底漆，其中底漆包含至少一种马来酸酐-接枝的聚烯烃聚合物。
在该方法中，在每种情况下，底漆用作通过熔融来焊接两种不同的聚烯烃塑料材料的助剂。由于采用了包含至少一种根据本发明的聚烯烃聚合物的底漆，在两个结合部件之间产生相容性，从而可以在两种塑料材料之间产生稳定和持久的整体连接。
可以采用各种方法将底漆施加至一个结合部件或两个结合部件的表面。例如，可以通过定量装置、针和定量机器人、注塑、挤出、膜涂、作为热熔体施加、喷射、铺展或者浸渍来进行施加。在所述方法中，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仅一个表面。在通过膜进行焊接的情况下，将膜插入两个基板之间。
如果底漆包含溶剂或者底漆用作乳液/分散体，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，从而剩下不粘的、尺寸稳定的底漆层。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高达几周。在施加之后，优选使底漆干燥至少一小时，优选至少12小时。
本发明的底漆的优点是在施加之后的仅几秒钟之后，底漆就可以焊接，并且焊接能力保持几周。当采用不含溶剂的底漆时，特别是作为热熔体时，更是如此。
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5,000μm，特别是100-3,000μm，优选500-1000μm。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。
在施加到待焊接基板的一个或两个表面之后，并且任选地在使底漆干燥之后，可以采用常规的焊接方法将待焊接基板互相连接。通常通过在结合面使结合部件局部塑化(plasticization)，以及通过加压结合来焊接塑料材料。选择工艺参数，使得熔体的显著的经挤压的流动导致结合部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]
通过热气流，通常是空气来进行对流加热，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，极性分子按照相应的高频磁场取向，一阶段法，仅用于极性塑料材料和膜
·振动焊接[VIB](线性；轨道的；旋转；角)
通过摩擦来加热，一阶段法
·激光焊接[LW](轮廓，同步，半同步，掩模)
通过辐射来加热，相干辐射，激光传输焊接，通常是一阶段法(可以是两阶段)
·红外焊接[IR]
通过辐射来加热，非相干辐射，两阶段法
任选地，也可以将上述焊接方法组合，例如，红外焊接和振动焊接。特别优选采用选自热板焊接、振动焊接、热接触或脉冲焊接、温气或热气焊接、微波或感应焊接的焊接方法，将聚丙烯塑料材料焊接至聚乙烯塑料材料。激光碰撞或穿透焊接、红外焊接、超声焊接和它们的组合，特别是选自红外焊接、振动焊接、热板焊接、超声焊接和它们的组合。
包含以下步骤的方法特别优选用于采用底漆将两种塑料材料整体结合：
·提供具有第一结合区的第一塑料材料，
●提供具有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，特别是在无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，特别是采用常规的塑料材料的焊接方法，例如红外焊接、热板焊接、热气焊接、振动焊接或超声焊接。
通常，DIN 1910-3:1977-09可用于焊接塑料材料。因此，这可以理解为借助热和/或压力，将热塑性材料整体结合。例如基于接触加热(通过固体元件焊接)，对流加热(通过温气焊接)，辐射加热(通过辐射焊接)，和通过摩擦的加热(通过移动焊接)，可以进行加热，以及可以通过电流进行焊接。
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，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影响。
将第一塑料材料预热对于第一结合区是有利的。可以将本领域技术人员已知的并且适于所述目的的助剂和技术用于预热。采用温气或等离子体特别适用于预热。通过辐射，特别是通过红外辐射或激光辐射来进行预热也是可以的。热板或被加热的工具也可用于预热第一结合区。最后，在加热炉中或在经加热的室(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。作为替代或者额外地，也可以仅在结合区本身预热。
在有利的方案中，在预热期间，加热装置与塑料材料之间的距离，特别是与待预热的第一结合区之间的距离，特别是加热装置的发射热量的区域或加热装置的释放热量的区域或加热装置的待被预热的活性表面或加热装置的与第一结合区相对的区域与塑料材料之间的距离，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热板接触，和/或在这种情形下进行加热。
另一个优点是，为第一结合部件选择塑料材料并且根据第一塑料材料调整方法参数，从而在预热期间，第一结合区熔融，并且在预热期间，在第一结合区产生熔体层。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改善的粘合和/或扩散和/或相互作用，以及某种流动，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，可以发生直至化学连接的与底漆的相互作用。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，从而组分不变形。通过采用合适的手段和/或方法步骤，优选可以补偿结合区与待施加的底漆之间的温差。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，在预热第一结合区的步骤之前将第一结合区预处理。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都是可能的预处理。也可以采用机械预处理，特别是通过刮擦、砂磨、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，可以通过电晕放电来进行电预处理，其中使第一结合区和/或第二结合区接受电的电晕放电，从而在相应的表面上得到极性分子。另外的可能性是等离子处理，优选采用等离子喷嘴来预处理结合区，特别是通过活化和/或清洁相应的表面来进行。通过等离子体来涂布也可以是有利的。另外的可能性是结合区的燃烧处理，从而在合适的塑料材料的情况下增加表面张力。另外形式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，特别是通过涂布油漆或采用助粘剂来进行预处理。将第一塑料材料或第一塑料材料的结合区域预处理，从而可以想象在预热之前的更长的时间间隔。例如，可以进行预处理作为第一塑料材料的制备方法的一部分，以便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，特别是在工业中，可以通过自动施加工具，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。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，也可以采用膜施加，其中，在第一步中，通过薄膜吹塑或流延膜挤出来由底漆制备膜。然后，例如通过切割或冲压方法，可以将膜修改成任何期望的形状，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，采用厚度为1μm-5000μm的膜/板是有利的。另外可以想到的实施方式有挤出焊接，其中底漆为焊丝的形式，或者在挤出机中熔融并且可以作为熔体施加至第一结合区。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。另外的可能性是通过喷射的方法施加底漆。在通过注塑进行施加的情况下，对注塑模具进行预处理和/或预热和/或温度的局部变化也是可以的。当然，本领域技术人员已知的并且适于具体实施的其他类型的施加也是可以的。
另外的优点是进一步加热第一结合区或在施加底漆期间加热第一结合区，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。这可以通过上述预热方法步骤进行，为了方便，在施加期间可以继续进行所述加热。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。例如，有利的是在施加期间加热第一结合区，例如通过同时辐射第一结合区、强制对流或接触加热来进行，以便防止第一结合区的温度在预热后下降。
在有利的方案中，施加底漆，从而厚度为1μm至5mm，优选10μm至3mm的连接层设置于第一结合区上。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。
另外的优点是通过第一结合区和计量装置的相对移动，通过计量装置将底漆施加到第一结合区，在施加底漆之前，通过第一结合区和加热装置的相对移动，通过加热装置预热向其施加底漆的第一结合区，当预热第一结合区时，通过计量装置施加底漆。
在这方面，已经证明有利的是，在预热期间，以10mm/min至100m/min，优选10mm/min至30m/min的速度引导加热装置通过第一结合区。
计量装置位于加热装置后面也可以是有利的，优选具有确定和恒定的间隔。特别有利的是以下述方式实施所述方法：通过计量装置和第一结合区以10mm/min至100m/min，优选10mm/min至30m/min的速度相对移动，通过计量装置将底漆施加至第一结合区，在施加底漆之前，通过加热装置和第一结合区的相对移动，通过加热装置预热向其施加底漆的所述结合区，施加底漆的计量装置或施加底漆的计量装置的喷嘴在同一时间位于加热装置的后面，具有0.1-10秒的时滞。
在这方面，已经发现有利的是，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，计量装置优选以固定和恒定的间距位于加热装置后面，以便确保在施加底漆之前即刻将第一结合区预热。当然，也可以想象在这方面调节间距，或者在对流预热的情况下，调节介质的体积流动速率和/或喷嘴直径，特别是采用合适的机械的、机电的或也可以是气动控制的调节器。
作为替代，涂布单元也可理解为是指作为两个完全独立或分离的组件的加热装置和计量装置，但是，它们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，将用于施加底漆的位置预热。
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基本相同的主要的相对移动或者具有基本相同的基础取向，除了所述主要的相对移动之外，两种特定的装置中的至少一种进行相对于塑料材料的额外的相对移动。例如，除了主要的相对移动之外，加热装置和/或计量装置也可以进行一种或多种次要的相对移动，在主要的相对移动期间，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以蜿蜒曲折的形状围绕主要的相对移动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。在所述方法中，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，或者另一方面塑料材料，可以是静止的，或者在每种情况下可以通过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，因此，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。这可以包括加热装置周围的区域或空间，其通过温度增加来影响温度，从而预热第一塑料材料的第一结合区。因此，例如可以避免过高的加热和损坏或劣化塑料材料。
还可以有利的是，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，提供具有总线接口特别是PROFIBUS或实时以太网接口的的加热装置。
在施加所述底漆之后，使第二结合区与底漆层接触。在这方面，可以有利的是，将两种塑料材料彼此固定，特别是通过本领域技术人员已知的夹紧装置或其他固定助剂。
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，预处理第二塑料材料或第二塑料材料的结合区从而在接触之前有更长的时间间隔。例如，可以想象的是，进行预处理作为第二塑料材料的制备方法的一部分，以便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可以预热第二结合区。在这阶段，上述实施方式也是优选的。
在第二结合区和底漆的上述接触之后进行结合方法，在所述方法中，采用供热将经处理和/或经涂布的结合部件塑化并且优选在压力的作用下彼此连接。对于第二结合区与底漆之间的所述整体连接，可以通过以下方式采用供热：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/振动或高频焊接；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、激光碰撞或激光穿透焊接，或也通过组合这些技术中的两种或更多种。
本发明的另外的目的是根据本发明的方法制备的制品或产品。
根据本发明的底漆用于焊接两种不同的聚烯烃塑料材料的用途也是本发明的目的。
实施例
所用的材料和缩写：
PP＝聚丙烯
PE＝聚乙烯
MAH＝马来酸酐
底漆1＝具有MFR的PE-(MD)-(MAH)(190℃；21.6Kg)＝12-22和具有MFR的PP-MAH(230℃；2.16Kg)＝7-12，以1:1重量/重量的比例复合
底漆2＝具有MFR的PE-(MD)-(MAH)(190℃；21.6Kg)＝12-22和具有MFR的PP-MAH(230℃；2.16Kg)＝7-12，以2:1重量/重量的比例复合
底漆3＝具有MFR的PE-(MD)-(MAH)(190℃；21.6Kg)＝12-22和具有MFR的PP-MAH(230℃；2.16Kg)＝7-12，以4:1重量/重量的比例复合
底漆4＝具有MFR的PE-(MD)-(MAH)(190℃；21.6Kg)＝12-22和Infuse 9808.15，以2:1重量/重量的比例复合(DOW Chemical Company)
测试燃料组成：
IR：红外焊接；VIB：振动焊接；
测试样品的制备：
为了制备底漆聚合物，以不同的比例预混合PE-(MD)-MAH和PP-MAH聚合物颗粒，将它们在注塑机的塑化单元(230℃)中熔化，并且复合和加工，以形成130mm x 70mm x 3mm的板。在下表中可以发现以为Kg单位的底漆的组成。
将板磨小至130mm x 68mm x 3mm，通过IR和振动焊接，将130mm x 3mm的表面焊接至PE和PP，直至挤满，在每种情况下，具有相同的表面积。在焊接之后24小时，从板的两端均磨掉8mm，将剩余的板切半(垂直于结合面切割)，并且通过在室温下以50mm/s的测试速度进行拉伸测试来测试。下表给出了底漆、塑料材料和所用的焊接方法、以及焊接的测试样品实现的拉伸强度(单位为MPa)的各个组合的结果：
结果显示，采用底漆编号2焊接的样品呈现出优异的拉伸强度。在这种情况下，(底漆编号2)PE和(底漆编号2)PP复合材料实现了大约19.13MPa的基本PE强度。因此，采用底漆，可以实现塑料材料PE和PP的特别是刚性焊接。
将以相同方式IR焊接的板在测试燃料FAM-B中在25℃储存14天，以便测试焊接连接的介质耐性。下表示出焊接和研磨的板在室温下和50mm/s的测试速度下的拉伸强度。
结果显示出焊接样品相对于测试燃料FAM-B的优异的耐老化性。
为了测试具有单独的底漆层的PE/底漆-聚合物/PP复合材料，将底漆2的130mm x3mm的板IR焊接至PP Sabic 4935。然后将底漆板磨小，从而在PP板上保留0.5mm的底漆层，并且底漆层焊接至也为130mm x 3mm的PE Lupolen GX5038BG25板。由此获得PE/(底漆2)/PP的结构。
在24小时之后，如上所述，在室温下，以50mm/s在拉伸测试中测试IR焊接的聚合物。
样品显示出15.14MPa的优异的拉伸强度。因此，当焊接PE和PP时，可以获得底漆2的优异强度。
PE-MAH和PP-MAH与六亚甲基二胺的反应：
在溶液中，使PE-MAH和PP-MAH与六亚甲基二胺反应。下表中列出了所用的反应物和溶剂的量。
在130℃，在500-ml的两颈烧瓶中，将PE-MAH和PP-MAH溶解在二甲苯中，然后，通过滴液漏斗，逐滴缓慢地引入溶解在20ml二甲苯中的胺。在回流2.5小时之后，将反应混合物倒到500ml水中，通过布氏漏斗过滤，并且用少量丙酮洗涤多次。在真空中干燥之后，获得无色固体。
通过温气，在PE Lupolen GX5038BG25和PP Sabic 4935上使获得的底漆聚合物熔融，在冷却之后测试粘附性。底漆5、6和7相对于PE和相对于PP显示出优异的粘附性。

Claims (11)

1.采用底漆焊接两种不同的聚烯烃塑料材料的方法，其中所述底漆包含至少一种马来酸酐-接枝的聚烯烃聚合物。
2.根据权利要求1所述的焊接方法，其特征在于，所述聚烯烃塑料材料的聚烯烃类聚合物可选自基于乙烯、丙烯和/或丁烯的聚-α-烯烃均聚物，特别是乙烯均聚物或丙烯均聚物，和基于乙烯、丙烯、1-丁烯、1-己烯和1-辛烯的聚-α-烯烃共聚物，特别是乙烯/α-烯烃共聚物和丙烯/α-烯烃共聚物，优选具有1-丁烯、1-己烯、1-辛烯或它们的组合的乙烯或丙烯的共聚物。
3.根据权利要求1或2所述的焊接方法，其特征在于，第一结合部件是聚乙烯-塑料材料，特别是HD聚乙烯、MD聚乙烯、LD聚乙烯、UHMW聚乙烯或LLD聚乙烯塑料材料，并且第二结合部件是聚丙烯塑料材料。
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，所述至少一种马来酸酐-接枝的聚烯烃聚合物选自马来酸酐-接枝的聚乙烯或马来酸酐-接枝的聚丙烯。
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，所述底漆包含马来酸酐-接枝的聚烯烃的混合物，特别是至少一种马来酸酐-接枝的聚乙烯和至少一种马来酸酐-接枝的聚丙烯的混合物。
6.根据权利要求5所述的焊接方法，其特征在于，至少所述不同的马来酸酐-接枝的聚烯烃聚合物的比例，特别是马来酸酐-接枝的聚乙烯与马来酸酐-接枝的聚丙烯的比例是0.2:1-20:1，特别是0.5:1-10:1，优选1:1-5:1，特别优选1.5:1-3:1。
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，基于所述至少一种马来酸酐-接枝的聚烯烃聚合物或它们的混合物，所述至少一种马来酸酐-接枝的聚烯烃或它们的混合物的马来酸酐含量为0.01-15重量％，特别是0.02-10重量％，优选0.05-8重量％，特别优选0.5-5重量％。
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，所述聚烯烃聚合物的至少一些马来酸酐基团与胺反应，所述胺特别是脂肪族胺，优选脂肪族二胺，例如六亚甲基二胺；优选根据本发明的聚合物或它们的混合物的5-100摩尔％，特别是10-80摩尔％，优选20-70摩尔％的马来酸酐基团与所述胺反应。
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，除了所述马来酸酐-接枝的聚烯烃聚合物之外，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。
10.根据权利要求1-9中任一项所述的焊接方法制备的制品。
11.根据权利要求1-9中任一项所述的底漆用于焊接两种不同的聚烯烃塑料材料的用途。
CN201680060610.8A 2015-10-16 2016-10-14 焊接两种不同的聚烯烃塑料的方法 Pending CN108136682A (zh)

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