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CN100450772C - 具有乙烯-乙烯醇共聚物层和保护层的多层复合材料 - Google Patents

具有乙烯-乙烯醇共聚物层和保护层的多层复合材料 Download PDF

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CN100450772C
CN100450772C CNB2005800012099A CN200580001209A CN100450772C CN 100450772 C CN100450772 C CN 100450772C CN B2005800012099 A CNB2005800012099 A CN B2005800012099A CN 200580001209 A CN200580001209 A CN 200580001209A CN 100450772 C CN100450772 C CN 100450772C
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layer
multilayer materials
acid
described multilayer
hexamethylene diamine
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CN1878671A (zh
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G·施米茨
H·黑格尔
H·里斯
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Evonik Operations GmbH
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Degussa GmbH
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Abstract

包括以下各层的多层复合材料具有改进的各层粘合性：I.选自氟聚合物模塑组合物和聚烯烃模塑组合物的内部层I；II.具有以下组成的粘结剂层II：a)0到80重量份多元胺-聚酰胺接枝共聚物，b)0到100重量份聚酰胺，c)0到85重量份选自氟聚合物和聚烯烃的聚合物，其中a)，b)和c)的重量份的总和为100，和，另外组分a)和b)的总和包括至少20重量份衍生自以下的单体单元：己内酰胺和/或以下组合：六亚甲基二胺/己二酸、六亚甲基二胺/辛二酸、六亚甲基二胺/癸二酸、六亚甲基二胺/十二烷二酸、六亚甲基二胺/间苯二甲酸或六亚甲基二胺/对苯二甲酸和d)至多50重量份选自冲击改性橡胶和常规辅助剂和添加剂的添加剂；III.包括EVOH模塑组合物的层III。

Description

具有乙烯-乙烯醇共聚物层和保护层的多层复合材料
本发明涉及具有阻隔层和保护层的多层复合材料，该阻隔层包括乙烯-乙烯醇共聚物(EVOH)，而该保护层包括形成防醇阻隔层并选自氟聚合物和聚烯烃的材料。
在例如作为管子在机动车辆中用于输送液体或气态介质的多层复合材料的发展中，所使用的模塑组合物必须对将要输送的介质具有足够的耐化学品性且该管子即使在长期暴露于燃料、油或热下之后必须能满足所有的对它们提出的力学要求。除了要求足够的耐油性之外，汽车工业还要求燃料管线具有改进的阻隔作用以降低烃类排放到环境中的量。多层管路体系的开发也就应运而生，其中例如EVOH用作阻隔层材料。此类体系例如描述在US 5 038 883、US 5 076 329和EP-A-1 216826中。然而，这些已知管子的缺点在于防醇阻隔作用不是令人满意的且内部层的防水阻隔作用也不令人满意，水随着时间会进入该EVOH层并导致防醇阻隔作用的进一步恶化。
为了解决该问题，EP-A-0 559 445建议施用氟聚合物层作为最内层。氟聚合物层和EVOH层通过粘结剂彼此连接。所公开的粘结剂是乙烯-丙烯酸酯共聚物、乙烯-醋酸乙烯酯共聚物、带有环氧基的聚烯烃和偏二氟乙烯和甲基丙烯酸甲酯的接枝共聚物。然而，证实这几乎没有实现任何粘合，持久粘合就更少了。由于所公开的成分中其中有一些是可溶于燃料的，这些偶联剂不具有令人满意的耐油性和耐热变形性。另外，本领域技术人员在EP-A-0 559 445的一般教导下不能容易地在这一方面重复该工作。
作为改进，聚烯烃系内部层还能提高防醇阻隔作用并，具体来说，阻挡水来保护EVOH。然而，也存在这样的问题，就是必须达到令人满意的粘合性。
因此，本发明的目的是开发使EVOH和氟聚合物或聚烯烃间的良好的粘合性成为可能的粘结剂。另一个目的是使粘结免受接触燃料的不利影响成为可能。另外，该粘结在该复合材料的使用期间应该维持在令人满意的程度。总的说来，非常简单的技术解决方案是所需的。
这些目的通过包括以下各层的多层复合材料来实现：
I：选自粘合改性或未改性的氟聚合物模塑组合物和粘合改性或未改性的聚烯烃模塑组合物的内部层I；
II：具有以下组成的粘结剂层II：
a)0到80重量份，优选1到60重量份，特别优选3到40重量份使用以下单体制备的接枝共聚物：
-基于该接枝共聚物计0.5到25wt％的具有至少4个、优选至少8个、特别优选至少11个氮原子和数均分子量Mn优选至少146g/mol、特别地优选至少500g/mol、非常特别优选至少800g/mol的多元胺，和
-选自内酰胺、ω-氨基羧酸和二胺和二元羧酸等摩尔组合(combinations)的形成聚酰胺的单体；
b)0到100重量份，优选10到75重量份，特别优选25到65重量份聚酰胺；
c)0到85重量份，优选5到75重量份，特别地优选10到65重量份，非常特别优选25到55重量份选自氟聚合物和聚烯烃的聚合物；
其中a)，b)和c)的重量份的总和为100，和，另外
-组分a)和b)的总和包括至少20重量份，优选至少40重量份，特别优选至少60重量份衍生自以下的单体单元：己内酰胺和/或以下组合：六亚甲基二胺/己二酸、六亚甲基二胺/辛二酸、六亚甲基二胺/癸二酸、六亚甲基二胺/十二烷二酸、六亚甲基二胺/间苯二甲酸或六亚甲基二胺/对苯二甲酸和
d)至多50重量份，优选至多30重量份，特别优选至多20重量份选自冲击-改性橡胶和常规辅助剂和添加剂的添加剂；
III.包括EVOH模塑组合物的层III。
该多层复合材料通常是管子或中空体。
用于层I的氟聚合物例如是聚偏二氟乙烯(PVDF)，乙烯-四氟乙烯共聚物(ETFE)，用第三组分如丙烯、六氟丙烯、乙烯基氟或偏二氟乙烯改性的ETFE(例如EFEP)，乙烯-三氟氯乙烯共聚物(E-CTFE)，聚三氟氯乙烯(PCTFE)，四氟乙烯-六氟丙烯-偏二氟乙烯共聚物(THV)，四氟乙烯-六氟丙烯共聚物(FEP)或四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)。
如果层II的粘结剂本身不含足够量的氟聚合物，则层I的氟聚合物优选是粘合改性的，即存在这样的官能团，它们能与粘结剂的氨基反应并因此使相的粘结成为可能。此类粘合改进通常以两种方法实现：
-或者该氟聚合物包含内部(built-in)官能团，例如酸酐基团或碳酸根(酯)基团，如US5 576 106、US-A-2003148125、US-A-2003035914、US-A-2002104575、JP-A-10311461、EP-A-0 726 293、EP A 0 992 518或者WO 9728394中所述。
-或者该氟聚合物模塑组合物包括这样的聚合物，其含有可与该氟聚合物混溶或者至少能与该氟聚合物相容的官能团。此类体系例如公开在EP-A-0 637 511或者美国相应专利US 5 510 160中和在EP-A-0 673 762或者美国相应专利US 5 554 426中，它们特意在此引入供参考。EP-A-0 673 762的改性氟聚合物包括：
-97.5到50wt％，优选97.5到80wt％，特别优选96到90wt％PVDF和
-2.5到50wt％，优选2.5到20wt％，特别优选4到10wt％包括至少以下基本结构单元的丙烯酸酯共聚物：
i)14到85wt％酯结构单元，
ii)0到75wt％酰亚胺结构单元，
iii)0到15wt％羧酸结构单元和
iiii)7到20重量份羧酸酐结构单元。
有关详细情形，读者可参考有关内容特意在此引入本专利申请公开内容中供参考的文件。
做为候选用于层I的聚烯烃可以首先是聚乙烯，尤其是高密度聚乙烯(HDPE)，或者是等规聚丙烯。该聚丙烯可以是均聚物或共聚物，例如能够使用乙烯或1-丁烯作为共聚单体，也能使用元规和嵌段共聚物。另外，该聚丙烯也可以是冲击-改性的，例如，如现有技术中公开的，用乙丙橡胶(EPM)或EPDM改性。
当层II的粘结剂本身不包含足够量的聚烯烃时，则层I的聚烯烃优选通过存在能与粘结剂的氨基反应的官能团来粘合改性。适合的官能团首先是羧基、羧酸酐基团、碳酸根(酯)基团、酰基内酰胺基团、噁唑啉基团、噁嗪基团、噁嗪酮基团、碳二亚胺基团或环氧基团。
如现有技术中所公开的，该官能团通常借助自由基和/或热通过与诸如丙烯酸、马来酸、富马酸、马来酸单丁基酯、马来酸酐、乌头酸酐、衣康酸酐或乙烯基噁唑啉的烯属不饱和官能团化合物反应而接枝于聚烯烃链上，或它们通过烯属不饱和官能团化合物与烯烃的自由基共聚而引入该主链中。
在组分II.a)的接枝共聚物的情况下，氨基浓度优选为100到2500mmol/kg。
作为多元胺，有可能使用例如以下类别的物质：
-多乙烯胺(
Figure C20058000120900071
Chemie Lexikon，第9版，第6卷，4921页，GeorgThieme Verlag Stuttgart 1992)；
-由交替聚酮制备的多元胺(DE-A 196 54 058)；
树型化合物(枝状体)，例如(H2N-(CH2)3)2N-(CH2)3)2-N(CH2)2-N((CH2)2-N((CH2)3-NH2)2)2(DE-A-196 54179)或三(2-氨乙基)胺、N，N-双(2-氨乙基)-N’，N’-双[2-[双(2-氨乙基)氨基]乙基]-1，2-乙烷二胺、3，15-双(2-氨乙基)-6，12-双[2-[双(2-氨乙基)氨基]乙基]-9-[2-[双[2-双(2-氨乙基)-氨基)乙基]氨基]乙基]-3，6，9，12，15-五氮杂十七烷-1，17-二胺(J.M.Warakomski，Chem.Mat.1992，4，1000-1004)；
-通过聚合4，5-二氢-1，3-噁唑并随后水解制备的线性聚乙烯亚胺(Houben-Weyl，Methoden der Organischen Chemie，第E20卷，1482-1487页，Georg Thieme Verlag Stuttgart，1987)；
-通过聚合氮丙啶制备的支化聚乙烯亚胺(Houben-Weyl，Methodender Organischen Chemie，第E20卷，1482-1487页，Georg ThiemeVerlag Stuttgart，1987)且该聚合物通常具有以下氨基分布：
25到46％伯氨基，
30到45％仲氨基和
16到40％叔氨基。
在优选的情况中，多元胺具有至多20000g/mol，特别优选至多10000g/mol，非常特别优选至多5000g/mol的数均分子量Mn。
用作形成聚酰胺的单体的内酰胺或ω-氨基羧酸含有4到19，尤其是6到12个碳原子。特别优选使用ε-己内酰胺、ε-氨基己酸、辛内酰胺、ω-氨基辛酸、月桂内酰胺、ω-氨基十二烷酸和/或ω-氨基十一烷酸。
二胺和二元羧酸的组合例如是六亚甲基二胺/己二酸、六亚甲基二胺/十二烷二酸、辛亚甲基二胺/癸二酸、癸亚甲基二胺/癸二酸、癸亚甲基二胺/十二烷二酸、十二亚甲基二胺/十二烷二酸和十二亚甲基二胺/2，6-萘二甲酸。另外，还有可能使用所有其它组合，例如癸亚甲基二胺/十二烷二酸/对苯二甲酸、六亚甲基二胺/己二酸/对苯二甲酸、六亚甲基二胺/己二酸/己内酰胺、癸亚甲基二胺/十二烷二酸/ω-氨基十一烷酸、癸亚甲基二胺/十二烷二酸/月桂内酰胺、癸亚甲基二胺/对苯二甲酸/月桂内酰胺或十二亚甲基二胺/2，6-萘二甲酸/月桂内酰胺。
在优选实施方案中，该接枝共聚物是追加使用低元羧酸来制备的，在每种情况下，基于其它形成聚酰胺的单体的总和计，低元羧酸选自0.015到大约3mol％二元羧酸和0.01到大约1.2mol％三元羧酸。在这些百分率中，单独地考虑在二胺和二元羧酸的当量组合中的各种单体二胺和二元羧酸。这样，该形成聚酰胺的单体总体上羧基稍微过量。如果使用二元羧酸，优选添加0.03到2.2mol％，特别优选0.05到1.5mol％，非常特别优选0.1到1mol％，尤其是0.15到0.65mol％；如果使用三元羧酸，优选使用0.02到0.9mol％，特别优选0.025到0.6mol％，非常特别优选0.03到1.4mol％，尤其是0.4到0.25mol％。同时使用低元羧酸不但显著地提高了耐溶剂和油性，尤其是耐水解和醇解性和耐环境应力开裂性，而且提高了溶胀行为和与此相关的尺寸稳定性以及防漫射阻隔作用。
作为低元羧酸酸，有可能使用具有6到24个碳原子的任何二元羧酸或三元羧酸，例如己二酸、辛二酸、壬二酸、癸二酸、十二烷二酸、间苯二甲酸、2，6-萘二甲酸、环己烷-1，4-二羧酸、均苯三酸和/或偏苯三酸。
另外，如果需要的话有可能使用具有3到50个碳原子的脂族，脂环族，芳族芳烷基和/或烷芳基取代的单羧酸，例如十二烷酸、不饱和脂肪酸、丙烯酸或苯甲酸作为调节剂。这些调节剂使得有可能降低氨基的浓度而不会改变分子的结构。另外，用这种方法能引入诸如双或三键等的官能团。然而，希望该接枝共聚物具有相当大比例的氨基。该接枝共聚物的氨基浓度特别优选为150到150mmol/kg，尤其是250到1300mmol/kg，非常特别优选300到1100mmol/kg。这里以及在下文中的术语“氨基”不但指端氨基而且指存在于多元胺中的任何仲或叔胺官能团。
这些接枝共聚物的制备更详细地描述在EP-A-1 065 048中。
组分II.b)的聚酰胺优选包括PA6、PA66、PA6/66、PA68、PA610、PA612、衍生自六亚甲基二胺以及间苯二甲酸和/或对苯二甲酸的聚酰胺、基于这些类型的共聚酰胺或它们的混合物。
PA6/66是由单体己内酰胺、六亚甲基二胺以及己二酸制备的共缩聚物。
作为能任选地作为组分II.c)的构分存在的氟聚合物和聚烯烃，有可能使用与层I相同的配混料。在这种情况下，当层I包括氟聚合物模塑组合物时，组分II.c)可同样包括氟聚合物(优选相同类型)，然而在这种情况下在组分II.c)中使用聚烯烃不会提高层的粘合性。
类似地，当层I包括聚烯烃模塑组合物时，组分II.c)同样可包括聚烯烃(优选相同类型)，然而在这种情况下在组分II.c)中使用氟聚合物不会提高层的粘合性。
任选存在于组分II.c)中的氟聚合物或聚烯烃优选如上所述是粘合改性的。在这种情况下，层I的模塑组合物的粘合改性可省去。
作为组分II.d)中的辅助剂和/或添加剂，有可能使用例如增塑剂、阻燃剂、稳定剂、加工助剂、层状硅酸盐、颜料、成核剂等。
EVOH早就是已知的。它是乙烯和乙烯醇的共聚物且有时还称为EVAL。该共聚物的乙烯含量通常为25到60mol％，尤其是28到45mol％。许多类型是市场上可买到的。例如，可参考公司手册“Introduction to Kuraray EVALTM Resins”，版本1.2/9810，来自Kuraray EVAL Europe。
除了层I～III之外，本发明复合材料中还可以存在另外的层，例如层V，其包括聚酰胺模塑组合物或聚烯烃模塑组合物并通过适合的粘结剂(层IV)连接到层III。适于这一目的的粘结剂是现有的。该聚酰胺或聚烯烃层还能通过包括橡胶或热塑性弹性体的壳层(sheathing)连接。另外的，最内部的氟聚合物或聚烯烃层可同样连接该内部层I。
在一个实施例中，该多层复合材料还包括回用料层。在根据本发明的复合材料的生产中，例如在挤塑装置的启动期间或在挤坯吹塑中以溢料形式、或在管子精加工(finishing)中时常会产生碎片。将由该碎片制成的回用料层嵌入两个其它层之间，这样能很好补偿该回用料共混物的脆性。
本发明多层复合材料例如是管子、充填口或容器，尤其是用于输送或储存液体或气体。这样的管子可以是平滑的或波纹形的或者仅在小段成为波纹形。波纹形管是现有技术(例如US 5 460 771)，因此在这个问题上不需要另外详述。此类多层复合材料的重要用途是用作燃料管线、槽充填口、蒸汽管线(即燃料蒸汽在其中输送的管线，例如排气管线)、灌装工位管线、冷却剂管线、空调器管线或者燃料容器(例如罐或槽)。
当本发明多层复合材料用于输送或储存易燃液体，气体或尘埃，例如燃料或燃料蒸汽时，最好使组成复合材料的层或附加的内部层导电。这可以通过使用所有现有技术中的方法混合导电添加剂来实现。作为导电性添加剂，有可能使用例如导电性炭黑、金属薄片、金属粉末、金属化玻璃球、金属化玻璃纤维、金属纤维(例如不锈钢的金属纤维)、金属化晶须、碳纤维(包括金属化碳纤维)、本身导电性聚合物或石墨纤丝。也可以使用各种导电性添加剂的混合物。
在优选情况下，该导电层直接接触输送或储存的介质且具有至多109Ω/平方(Ω/square)，优选至多106Ω/平方的表面电阻。测定多层管电阻的测量方法描述在SAE J 2260(1996年11月，7.9节)中。
该多层复合材料可以以一个或多个步骤制造，例如通过单步骤工艺使用多组分注塑法、共挤塑法、共挤吹塑法(例如还有3D吹塑、将型坯挤压进入敞模瓣中、3D型坯操作、抽吸吹塑(suction blowmolding)、3D抽吸吹塑、连续吹塑)或通过多步骤工艺，例如涂覆。
以下将通过实施例来说明本发明。在实施例中，使用以下模塑组合物：
内部层(层I)：
氟聚合物1：如EP-A 0 673 762中所述的混合物，由95wt％市售PVDF和5wt％聚戊二酰亚胺组成，该聚戊二酰亚胺由以下基本结构单元构成：
57wt％衍生自甲基丙烯酸甲酯，
30wt％N-甲基-戊二酰亚胺类，
3wt％衍生自甲基丙烯酸，和
10wt％戊二酸酐类(通过使甲基丙烯酸甲酯与在熔体状态下的甲胺的水溶液反应来制备)
氟聚合物2：NEOFLON
Figure C20058000120900101
RP 5000，来自Daikin Industries Ltd.，Japan，改性EFEP
氟聚合物3：NEOFLON
Figure C20058000120900111
RP 5000 AS，来自Daikin Industries Ltd.，Japan，已成为导电的改性EFEP
聚烯烃1：STAMYLAN
Figure C20058000120900112
P 83 MF 10，来自DSM Deutschland GmbH的PP共聚物
聚烯烃2：VESTOLEN
Figure C20058000120900113
A 6013，来自DSM Deutschland GmbH的HDPE
粘结剂(层II和IV)：
接枝共聚物的制备：
将9.5kg月桂内酰胺于升温容器中在180℃-210℃下熔融并转入压力-分级的缩聚容器中；随后添加475g水和0.54g次磷酸。在自生压力下，内酰胺在280℃离解；然后在3小时的期间内将混合物减压到残留水蒸气压为5巴，并添加500g聚乙烯亚胺(来自BASF AG，Ludwigshafen的LUPASOL G 100)和15g十二烷二酸。在自生压力下同时混合两个成分；随后将混合物减压到大气压，然后在280℃于该熔体上方通过氮气2小时。借助熔体泵以线料形式排出透明熔体，在水浴中冷却并随后造粒。
HV 1：在双螺杆混配机(来自Berstorff的ZE 25 33D，270℃，150rpm，通过量为10kg/h)上熔融混合12.6kg PA6(来自BASF AG的ULTRAMID
Figure C20058000120900114
B4)、22.82kg氟聚合物2和5.0kg接枝共聚物，挤出并造粒。
HV 2：PA6(来自BASF AG的ULTRAMIDB4)
HV 3：类似HV 1，除了氟聚合物2用接枝有马来酸酐的聚丙烯(来自Mitsui Chemicals Inc.，Japan的ADMER
Figure C20058000120900116
QB 520 E)代替
HV 4：类似HV 1，除了氟聚合物2用接枝有马来酸酐的聚乙烯(来自Mitsui Chemicals Inc.，Japan的ADMER
Figure C20058000120900117
NF 408 E)代替
HV 5：用双螺杆挤压机Berstorff ZE 25在280℃制备自35.3wt％VESTAMID
Figure C20058000120900118
D22(来自Degussa AG的PA612)、48.1wt％ULTRAMID
Figure C20058000120900119
B5W(来自BASF AG的PA6)、10.7wt％接枝共聚物和5.4wt％EXXELOR
Figure C200580001209001110
VA1803(来自EXXON的用马来酸酐官能化的乙丙橡胶)的均质混合物，以线料形式挤出，造粒并干燥。
EVOH层(层III)：EVAL
Figure C200580001209001111
F101，来自KURARAY的EVOH，含有32mol％乙烯
外层(层V)：
PA12：来自Degussa AG的冲击-改性，增塑聚酰胺(VESTAMID
Figure C20058000120900121
X 7293)
聚烯烃2：如上
实施例1到5：
在装备有两个45型挤塑机和三个30型挤塑机的5-层装置上以大约12m/min的挤出速度生产尺寸为8x1mm的管子。
 实施例 内部层＝层I 层II  层III 层IV  层v
 1 0.1mm氟聚合物1 0.2mmHV 2  0.1mmEVOH 0.2mmHV 5  0.4mmPA 12
 2 0.1mm氟聚合物2 0.2mmHV 1  0.1mmEVOH 0.2mmHV 5  0.4mmPA 12
 3 0.1mm氟聚合物3 0.2mmHV 1  0.1mmEVOH 0.2mmHV 5  0.4mmPA 12
 4 0.1mm聚烯烃1 0.2mmHV 3  0.1mmEVOH 0.2mmHV 5  0.4mmPA 12
 5 0.1mm聚烯烃2 0.2mmHV 4  0.1mmEVOH 0.2mmHV 4  0.4mm聚烯烃2
管子的特征：
在实施1～5的管子的情况下，内部氟聚合物或聚烯烃层与EVOH层间的粘合性高到当刚挤出时和在燃料中储存(使用CM 15的内部接触储存，即，测试燃料由42.5体积％异辛烷、42.5体积％甲苯和15体积％甲醇组成，在80℃，每周更换一次燃料，1000h)之后复合材料都不会分离。
根据SAE J 2260，在-40℃下的低温冲击韧性测试中，所有管子当刚挤出时和在燃料中储存(使用CM 15在80℃的内部接触储存，每周更换一次燃料，1000h)之后的破裂率都是0/10。

Claims (18)

1.包括以下各层的多层复合材料，
I：选自氟聚合物模塑组合物和聚烯烃模塑组合物的内部层I；
II：具有以下组成的粘结剂层II：
a)0到80重量份使用以下单体制备的接枝共聚物
-基于该接枝共聚物计0.5到25wt％具有至少4个氮原子的多元胺和
-形成聚酰胺的单体，其选自内酰胺、ω-氨基羧酸以及二胺和二元羧酸的等摩尔混合物；
b)0到100重量份聚酰胺；
c)0到85重量份选自氟聚合物和聚烯烃的聚合物；
其中a)，b)和c)的重量份的总和为100，和，另外
-组分a)和b)的总和包括至少20重量份衍生自以下的单体单元：己内酰胺和/或以下组合：六亚甲基二胺/己二酸、六亚甲基二胺/辛二酸、六亚甲基二胺/癸二酸、六亚甲基二胺/十二烷二酸、六亚甲基二胺/间苯二甲酸或六亚甲基二胺/对苯二甲酸和
d)至多50重量份选自冲击改性橡胶和常规辅助剂和添加剂的添加剂；
III：包括EVOH模塑组合物的层III。
2.权利要求1所述的多层复合材料，其中
-该组分IIa)的存在量为1到60重量份和/或
-该组分IIb)的存在量为10到75重量份。
3.权利要求1所述的多层复合材料，其中
-该组分IIa)的存在量为3到40重量份和/或
-该组分IIb)的存在量为25到65重量份。
4.上述权利要求中任一项所述的多层复合材料，其中存在5到75重量份组分IIc)。
5.权利要求4所述的多层复合材料，其中存在10到65重量份组分IIc)。
6.权利要求4所述的多层复合材料，其中存在20到55重量份组分IIc)。
7.权利要求1-3中任一项所述的多层复合材料，其中该氟聚合物选自PVDF，ETFE、用丙烯、六氟丙烯、乙烯基氟或偏二氟乙烯改性的ETFE、E-CTFE、PCTFE、THV、FEP和PFA。
8.权利要求1-3中任一项所述的多层复合材料，其中所述聚烯烃是聚乙烯或等规聚丙烯。
9.权利要求1-3中任一项所述的多层复合材料，其中该氟聚合物或聚烯烃是粘合改性的。
10.权利要求1-3中任一项所述的多层复合材料，其中组分IIb的聚酰胺包括PA6、PA66、PA6/66、PA68、PA610、PA612、衍生自六亚甲基二胺和间苯二甲酸和/或对苯二甲酸的聚酰胺或它们的混合物。
11.权利要求1-3中任一项所述的多层复合材料，它还具有这样的层，该层包括聚酰胺模塑组合物或聚烯烃模塑组合物并通过适合的粘结剂连接到层III。
12.权利要求1-3中任一项所述的多层复合材料，它是中空体。
13.权利要求1-3中任一项所述的多层复合材料，它是整体成波纹形的或子区成波纹形的管子。
14.权利要求1-3中任一项所述的多层复合材料，它是燃料管线、制动液管线、冷却剂管线、液压液管线、灌装工位管线、空调器管线、蒸汽管线、容器或充填口。
15.权利要求1-3中任一项所述的多层复合材料，其中组成该复合材料的备层之一或附加的内部层已制成导电的。
16.权利要求1-3中任一项所述的多层复合材料，它通过共挤塑、涂覆或多组分注塑来制备。
17.权利要求1-3中任一项所述的多层复合材料，它是管子。
18.权利要求1-3中任一项所述的多层复合材料，它通过共挤吹塑来制备。
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