CN103124638B - 具有用于结合至金属基材的接枝组合物的连接层粘合剂 - Google Patents

具有用于结合至金属基材的接枝组合物的连接层粘合剂 Download PDF

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CN103124638B
CN103124638B CN201180046959.3A CN201180046959A CN103124638B CN 103124638 B CN103124638 B CN 103124638B CN 201180046959 A CN201180046959 A CN 201180046959A CN 103124638 B CN103124638 B CN 103124638B
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graft
polyolefin
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adhesive
olefin elastomer
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CN103124638A (zh
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M.G.博特罗斯
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Equistar Chemicals LP
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Abstract

公开了具有用于结合至金属基材的接枝组合物的连接层粘合剂。该接枝组合物由活性接枝聚烯烃与烯烃弹性体的反应产物构成。所述接枝聚烯烃通过首先加热聚烯烃和不饱和单体制备。活性接枝聚烯烃与烯烃弹性体的进一步反应提供了接枝组合物。通过烯烃弹性体的存在和额外的反应步骤的使用，接枝效率显著提高。当配制成连接层粘合剂时，所述接枝组合物提供了改善的与金属基材的结合。

Description

具有用于结合至金属基材的接枝组合物的连接层粘合剂
相关申请的交叉引用
本申请要求于2010年9月29日提交的美国申请12/924,540的优先权，并以引用的方式将所述美国申请以其整体并入。
技术领域
本公开涉及接枝组合物，特别是在连接层粘合剂（tie-layer adhesives）中用于改善与金属基材的结合的组合物。
背景技术
连接层粘合剂用于在多层、共挤出结构中将聚烯烃结合至不同基材，特别是用于吹塑膜材和流延膜材、挤出涂覆、吹塑、片材挤出、线缆、管材、和其他工业应用。连接层粘合剂通常包含作为主要组分的聚烯烃基础树脂，和接枝聚烯烃。在使用或不使用自由基引发剂的情况下，通过在升高的温度下使聚烯烃与不饱和单体反应来制备接枝聚烯烃。市售的连接层粘合剂包括Plexar ®树脂，Equistar Chemicals, LP的产品，其为酸酐改性的聚烯烃。
除了所述基础树脂和接枝聚烯烃之外，连接层粘合剂通常还包含其他聚合物树脂或添加剂以提供更好的粘合性、透明度或其他益处。通常，存在折衷。例如，改进粘合性的改性通常降低透明度，反之亦然。
弹性体——无规或嵌段共聚物——通常包含在连接层粘合剂组合物中，以改善相容性、提高粘合性或给予其他益处。例如，基于苯乙烯的嵌段共聚物已经被用于改进多层构造中的粘合性，所述多层构造要求将聚乙烯结合至苯乙烯系聚合物（美国专利申请公开2007/0071988和2007/0167569号）。
其他通常使用的弹性体包括烯烃弹性体，如乙丙橡胶(EPR)或三元乙丙橡胶(EPDM)。很多文献教导将烯烃弹性体与其他连接层粘合剂组分共混（参见例如美国专利申请公开2004/0097637、2008/0032148、2009/0035594和2010/0174036号），但这些文献都没有建议在制备接枝聚烯烃过程中使烯烃弹性体与接枝聚烯烃反应。
多层膜材的透明度通常是问题，特别是用于食品包装工业。用于肉和乳酪、零食、烘焙混合料、和很多其他用途的包裹需要阻隔层（例如，EVOH、聚酰胺、聚烯烃）来防止氧气和/或水汽透过，并且制造具有高透明度的这类结构是巨大的挑战。添加剂如美国专利申请公开2007/0054142号的双环改性剂有时用于改善透明度而不牺牲粘合性。
美国专利申请公开2010/0174036号教导了用于具有有利的透明度和粘合性平衡的多层膜材的连接层粘合剂可以通过将接枝（“马来酸酐接枝”(maleated)）聚烯烃、聚烯烃弹性体和LLDPE依次共混来制备。同样，没有建议使聚烯烃弹性体与接枝聚烯烃反应。
需要适合在制备具有良好粘合性和高透明度的多层结构中使用的改进的连接层粘合剂组合物。有价值的方式能避免昂贵的添加剂和性能折衷。理想地，改进的连接层粘合剂可以使用经济的起始材料、通常使用的装备和类似技术来制备。
发明内容
一方面，本公开涉及在连接层粘合剂中使用的接枝组合物（下文中有时也称为“接枝[聚烯烃/弹性体]组合物”），该连接层粘合剂具有改善的与金属基材的结合。所述组合物包含活性（live）接枝聚烯烃与烯烃弹性体的反应产物。另一方面，本发明涉及用于制备接枝组合物的方法。所述方法包括在有效制备活性接枝聚烯烃的条件下加热聚烯烃和不饱和单体，然后再使所述接枝聚烯烃和任何残余聚烯烃和/或不饱和单体与烯烃弹性体反应。出乎意料的是，通过烯烃弹性体的存在和额外的反应步骤的使用，接枝效率显著提高。本发明包括包含接枝组合物的连接层粘合剂和引入该粘合剂的多层膜材和片材。当以相对低浓度配制成连接层粘合剂时，所述接枝组合物获得了具有出乎意料地改善的与金属基材的结合的多层结构。
附图说明
参照以下附图，以示例性的方式描述了本申请的实施方案，其中：
图1例示了本申请实施例中描述的连接层1和作为对比的连接层2的环剥离测试结果。
具体实施方式
本发明的接枝组合物包含活性接枝聚烯烃和烯烃弹性体的反应产物。
在使用或不使用自由基引发剂的情况下，在能够有效将不饱和单体单元接枝在聚烯烃骨架上的条件下，通过在升高的温度下使聚烯烃与不饱和单体反应来制备适合于在制备接枝组合物中所使用的活性接枝聚烯烃。
适合于制备活性接枝聚烯烃的聚烯烃包括高密度聚乙烯(HDPE)、中等密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、聚丙烯、乙烯-丙烯共聚物、冲击性改性的聚丙烯等、及它们的共混物。用于制备接枝聚烯烃的优选的聚烯烃为聚乙烯，特别是HDPE和LLDPE，特别是HDPE。
不饱和单体与聚烯烃反应以制备接枝聚烯烃。合适的不饱和单体也是公知的。优选的不饱和单体为烯属不饱和羧酸及酸衍生物，特别是酯、酸酐、酸盐等。实例包括丙烯酸、甲基丙烯酸、马来酸、富马酸、衣康酸、柠庚酸、马来酸酐、四氢邻苯二甲酸酐、降冰片-5-烯-2,3-二甲酸酐、桥亚甲基四氢邻苯二甲酸酐、降冰片烯二酸酐等、及它们的混合物。马来酸酐是特别优选的。其他合适的不饱和单体记载于美国专利申请公开2004/0097637和2007/0054142号中，其教导以引用的方式并入本文中。
所使用的不饱和单体和聚烯烃的相对用量可以不同并取决于多种因素例如聚烯烃和不饱和单体的性质、反应条件、可用的装置和其他因素。通常，以所制备的活性接枝聚烯烃的量计，不饱和单体用量在0.1-15重量%、优选0.5-6重量%、且最优选1-3重量%的范围内。
接枝根据已知工艺完成，通常通过加热聚烯烃与一种或多种不饱和单体的混合物进行。最普遍地，通过在施加剪切的（shear-imparting）挤出机/反应器中将聚烯烃和不饱和单体熔融共混来制备接枝聚烯烃。双螺杆挤出机如由Coperion以型号ZSK-53、ZSK-83、ZSK-90和ZSK-92市售的那些尤其适用于进行接枝步骤。可以使用自由基引发剂如有机过氧化物但不是必要的。
用以生成活性接枝聚烯烃的不饱和单体与聚烯烃的接枝在升高的温度下、优选在180℃-400℃、更优选在200℃-375℃、并最优选在230℃-350℃的范围内进行。挤出机中的剪切速率可以在宽范围内、优选在30-1000 rpm、更优选在100-600 rpm、并最优选在200-400 rpm范围内变化。
通过“活性接枝聚烯烃”，我们是指能够与添加的烯烃弹性体和用于制备该接枝聚烯烃的任何残余聚烯烃、不饱和单体、和/或自由基引发剂进一步反应的接枝聚烯烃。市售的接枝聚烯烃不是“活性的”，因为自由基成分已经反应掉了或已经在产物整理(workup)期间通常在造粒期间淬灭了。活性接枝聚烯烃含有通过减粘裂化热生成的或来自过氧化物分解的活性自由基物质。通过新制得的接枝聚烯烃（通常在仍处于熔融态时）与添加的烯烃弹性体的结合，残余的自由基成分使得反应能够继续。接枝聚烯烃、烯烃弹性体、残余聚烯烃和残余不饱和单体中的一种或多种可以参与到这个二次反应中。
因此，在制备接枝组合物的第二工艺步骤中，所述活性接枝聚烯烃（和任何残余聚烯烃和/或不饱和单体）与烯烃弹性体反应。该反应可以使用任何合适的反应器进行。合宜地，通过在如前所述的施加剪切的挤出机/反应器中使新制得的活性接枝聚烯烃与烯烃弹性体结合来进行所述反应。在一种特别优选的方式中，所述活性接枝聚烯烃直接从第一挤出机出口转移（仍处于熔融态时）至第二挤出机，在第二挤出机中发生与烯烃弹性体的反应。
所使用的烯烃弹性体的量取决于弹性体和接枝聚烯烃的性质、期望的连接层特性、反应条件、装置和其他因素。然而，以所制备的接枝组合物的量计，弹性体的用量通常在5-60 重量%、更优选20-50重量%、并最优选30-40重量%的范围内。
所述活性接枝聚烯烃和烯烃弹性体在升高的温度下、优选在120℃-300℃、更优选在135℃-260℃、并最优选在150℃-230℃的温度下反应。优选地，用来制备这种接枝组合物的反应温度低于用来制备活性接枝聚烯烃的温度。用于这个步骤的挤出机中的剪切速率可以在宽范围内、优选在30-1000 rpm、更优选在100-600 rpm、并最优选在200-400 rpm范围内变化。
所得的接枝[聚烯烃/弹性体]组合物合宜地在这个点被淬灭并造粒，但如下文进一步描述的，它可以在制成之后立即与基础树脂结合。
合适的烯烃弹性体包括乙丙橡胶(EPR)、三元乙丙橡胶(EPDM)等、及它们的混合物。如本文中所使用的，“弹性体”是指具有橡胶样特性和小结晶度或没有结晶度的产品。优选地，所述烯烃弹性体含有10-80重量%的乙烯重复单元。更优选的烯烃弹性体含有10-70重量%的乙烯单元。市售的烯烃弹性体包括Lanxess Corporation的Buna® EP T2070 (68%乙烯、32% 丙烯)；Buna EP T2370 (3% 亚乙基降冰片烯、72%乙烯、25%丙烯)；Buna EP T2460 (4% 亚乙基降冰片烯、62%乙烯和34%丙烯)；ExxonMobil Chemical的Vistalon® 707 (72%乙烯、28%丙烯)；Vistalon 722 (72%乙烯、28%丙烯)；和Vistalon 828 (60%乙烯、40%丙烯)。合适的乙烯-丙烯弹性体还包括ExxonMobil Chemical的Vistamaxx®弹性体，特别是等级6100、1100和3000的弹性体，和Dow Chemical的Versify®弹性体，特别是等级DP3200.01、DP3300.01和DP3400.01的弹性体，其乙烯含量分别为9、12和15重量%。另外的EPDM橡胶包括Dow的NordelTM烃橡胶，例如3722P、4760P和4770R等级的烃橡胶。
意外地发现，当活性接枝聚烯烃与烯烃弹性体进一步反应时，能够实现高接枝效率。通常，聚烯烃接枝进行得比定量少。例如，在用于将马来酸酐接枝在高密度聚乙烯上的常规方法中，效率通常为80-85%。相比之下，当活性接枝聚烯烃进一步与烯烃弹性体反应时，能够实现不饱和单体的几乎定量的转化。
优选地，将至少90重量%、更优选至少95重量%、并最优选至少98重量%的不饱和单体引入接枝组合物中。根据本领域中公知的方法，可以通过湿化学法（滴定法等）或更优选通过傅里叶变换红外光谱法(FTIR)测量所引入的量。
所述接枝组合物是连接层粘合剂的有价值组分。本发明的连接层粘合剂包含2-50重量%的接枝[聚烯烃/弹性体]和50-98重量%的基础树脂（也称为“稀释(let-down)”树脂）。更优选的连接层粘合剂包含5-30重量%的接枝组合物和70-95重量%的基础树脂。最优选的粘合剂包含15-25重量%的接枝组合物和75-85重量%的基础树脂。后文详细阐述的接枝组合物的优点是在连接层粘合剂中使用相对低的浓度同时实现良好的粘合性的能力。
合适的用于连接层粘合剂的基础树脂包括乙烯均聚物；乙烯与C3-C8 α-烯烃、羧酸乙烯酯和丙烯酸烷基酯的共聚物；乙烯和丙烯与二烯单体的三聚物；丙烯均聚物；聚异丁烯；和异丁烯与异戊二烯的共聚物。乙烯均聚物和共聚物可以包括LDPE；MDPE；HDPE；LLDPE；非常低密度聚乙烯；超低密度聚乙烯；乙烯-乙酸乙烯酯(EVA)共聚物；乙烯-丙烯酸酯共聚物如乙烯-丙烯酸乙酯共聚物和乙烯-丙烯酸正丁酯共聚物；及它们的共混物。
LLDPE是优选的基础树脂。特别地，所述LLDPE优选为乙烯与1-丁烯、1-己烯或1-辛烯的共聚物。优选地，所述LLDPE的密度在0.895-0.925 g/cm3的范围内，并且熔体指数(MI2)在0.5到5 g/10 min，更优选在0.8-2.5 g/10 min的范围内。合适的LLDPE基础树脂包括Petrothene® GA502、GA503、GA602和GA616系列树脂，其为Equistar Chemicals, LP的产品。
在优选的方面，用于制备接枝[聚烯烃/弹性体]组合物的方法与用于制备基础树脂的方法整合。在这种方法中，新制得的聚乙烯粉末（例如LLDPE）与接枝组合物在线(in-line)共混以生成用作母料或用作连接层粘合剂的混合物。所述接枝组合物可以为粒料形式，或者可以在制成接枝组合物之后立即与基础树脂粉末结合。在任一情况下，“在线”方法获得了具有减少的热历程和时常改善的特性的产品（参见美国专利7,064,163号，其教导以引用的方式并入本文中）。
除了所述基础树脂和接枝组合物之外，所述连接层粘合剂还可以包含其他常用组分，包括粘合促进剂、弹性体聚合物、UV抑制剂、抗氧化剂、热稳定剂等。关于这些的某些实例，参见美国专利申请公开2004/0097637号，其教导以引用的方式并入本文中。
特别优选的连接层粘合剂包含5-30重量%、优选15-25%的特定接枝组合物和70-95重量%、优选75-85重量%的作为基础树脂的LLDPE。通过将马来酸酐接枝在HDPE上，然后使所述活性接枝聚烯烃与EPR或EPDM特别是EPR进一步反应来制备这种接枝组合物。，这样的组合物采用比EPR或EPDM与接枝HDPE简单共混时通常需要的量更少的接枝材料提供了良好的粘合性和高透明度。
连接层粘合剂对于在多层结构特别是膜材、片材、管材或其他产品中结合不同材料是有价值的。特别地，所述粘合剂用于结合塑料、木材、玻璃、纸张、复合材料和金属基材。它们可以在层合、挤出（或共挤出）、片材挤出、挤出涂覆、注塑、吹塑、熔体热成型和其他工艺中使用。
特别地，已经发现本文中公开的连接层粘合剂组合物提供了更强的与金属基材的结合。优选的基材为金属，包括金属氧化物和合金。合适的金属包括周期表中第1-6行的第1-16族的那些。金属可以包括碱金属、碱土金属、过渡金属和第13-16族的贫金属（post transition metal）元素。优选的金属包括周期表的第1-4行中的那些。特别优选的金属包括铝、锡、锌、镍、铜、铂、金、银、钯、铬、钴、钢或铁和它们的混合物。另外的优选的合金包括黄铜、青铜、钢。本文中所公开的金属可以和非金属化合物一起被包含以形成复合材料。
在一些实施方案中，当在90℃的温度下以50 mm/min从金属基材上扯下5”×2” 1”的连接层粘合剂条带时，结合至金属基材的连接层的粘合剂强度为120 N/10mm或更大，可选择地为135 N/10mm或更大，且可选择地为150 N/10mm或更大，可选择地为160 N/10mm，可选择地在120-185 N/10mm的范围，可选择地在135-170 N/10mm的范围，可选择地在150-160 N/10mm的范围（参见实施例）。
对于制备在多种应用中使用的多层聚烯烃/金属结构，所述粘合剂是特别有价值的，所述应用例如多层管材应用、建筑板材和卡车板材应用。所述粘合剂还可以用于膜材和片材，包括阻隔膜材。除了将其他层结合在一起的粘合剂层之外，所述多层膜材还具有至少两层。通常，至少一层用作阻隔层。通常通过共挤出制备的多层膜材时常包括聚烯烃层如LDPE、LLDPE、HDPE、EVA、乙烯-丙烯酸共聚物、乙烯-甲基丙烯酸共聚物、乙烯-丙烯酸酯共聚物、乙烯-甲基丙烯酸酯共聚物、离聚物等。所使用的阻隔树脂通常为乙烯-乙烯醇(EVOH)或聚酰胺树脂如尼龙。
多层阻隔膜材广泛地用于食物包装，并且在这些应用的大多数中，透明度和高粘合性是重要的。食品包装应用包括用于包装肉和禽制品的成型的包袋(bag)、口袋(pouch)和套袋(casing)。它们也可以用于零食、谷物、烘焙混合料等。它们也可以具有用于烹饪包装的用途。
对在多层阻隔结构中的粘合剂层和阻隔层之间的界面的分析揭示出本发明的连接层的有利特性。例如扫描电子显微镜(SEM)在粘合剂-EVOH界面上显示出紧密的、基本无缝的结合。作为替代用接枝HDPE与EPR的共混物来制备粘合剂时，所述界面凸起并且更明显。当使用原子力显微镜(AFM)分析界面时，区别也明显。本发明的连接层能够提供光滑的、未扰乱的、几乎无缺陷的界面，其符合良好的粘合性和高透明度。相比之下，当接枝HDPE与EPR的共混物用于制备粘合剂时，AFM示出所述界面在粘合剂层和阻隔层之间包括离散的相间区域，其符合良好的粘合性但可能也造成较低的透明度。
本发明的连接层粘合剂可以在众多多层阻隔膜材构造中使用，所述多层阻隔膜材构造包括具有五层、七层、九层或更多层的结构。示例的多层构造包括以下结构，其中"FCL"代表食物接触层如LDPE、LLDPE、EVA、乙烯-丙烯酸或酯共聚物、乙烯-甲基丙烯酸或酯共聚物、离聚物等：
HDPE /粘合剂/ EVOH /粘合剂/ HDPE，
HDPE /粘合剂/聚酰胺/粘合剂/ HDPE，
EVOH /粘合剂/ HDPE /粘合剂/ EVOH，
LDPE /粘合剂/聚酰胺/粘合剂/ FCL，
LDPE /粘合剂/ EVOH /粘合剂/ FCL，
LLDPE /粘合剂/ EVOH /粘合剂/ FCL，
LLDPE /粘合剂/聚酰胺/粘合剂/ FCL，
HDPE /粘合剂/ EVOH /粘合剂/ FCL，
HDPE /粘合剂/聚酰胺/粘合剂/ FCL，
一些常用的可密封膜材构造包括：
LLDPE /粘合剂/ EVOH /粘合剂/ 密封剂，
HDPE /粘合剂/聚酰胺/粘合剂/密封剂，
HDPE /粘合剂/ EVOH /粘合剂/密封剂，
其中密封剂层为例如EVA、LLDPE或离聚物。
当使用金属基材时，这样的结构内部可以包含：
PO/粘合剂/ M /粘合剂/ PO，
M/粘合剂/ PO /粘合剂/ M，
其中PO为聚烯烃层，如LDPE、LLDPE、HDPE等，并且M为金属或金属合金。
可以将添加剂如防雾组分加入多层结构，特别是具有外部聚烯烃层的多层结构。合适的防雾组分包括具有约8至约20个碳原子的饱和或不饱和脂肪酸的甘油单酯、具有约8至约20个碳原子的饱和或不饱和脂肪酸的甘油二酯和末端具有磷酸根、硫酸根或季铵官能团的离子型表面活性剂。
合适作为防雾组合物的还有包括阴离子型、阳离子型、非离子型和两性型表面活性剂的表面活性剂。合适的离子型表面活性剂在末端具有磷酸根、硫酸根或季铵官能团。其他防雾组合物包括脂肪族羧酸的脱水山梨糖醇酯、脂肪族羧酸的甘油酯、其他多元醇与脂肪族羧酸的酯、聚氧化乙烯化合物如脂肪族羧酸的聚氧化乙烯脱水山梨糖醇酯和高级脂肪族醇的聚氧化乙烯醚。如US 6,726,968中所公开的加入合适的防雾剂。
下文的实施例仅是示例性的。本领域那些技术人员将意识到很多变体和实施方案可以被使用并与本公开一致。
组分(A)：接枝-1 [HDPE/EPR]组合物
接枝-1为活性接枝聚烯烃，通过将高密度聚乙烯（密度：0.957 g/cm3)和马来酸酐(以添加的反应物总量计2.0重量%)进料至具有在450oF-660oF（230-350℃）范围内的温度下加热并在200-400 rpm范围内的剪切速率下操作的区域的第一Coperion® ZSK-92双螺杆挤出机中来制备，以产生活性接枝聚烯烃。反应完成之后，所述活性接枝聚烯烃中引入的马来酸酐含量为1.9重量%并且MI为9g/10min。
接枝-1离开第一挤出机并立即进入第二ZSK-92双螺杆挤出机，在其中与乙丙橡胶即EPR-1结合并反应。EPR-1为Nordel® 3722（Dow Chemical的产品，具有72重量%的乙烯重复单元）。第二挤出机中的条件：温度范围：300oF-450oF (150-230℃)；剪切速率：200-400 rpm。将所得的接枝[HDPE/EPR]产品冷却并造粒。
通过这种方法，采用35%的EPR-1配制接枝组分(A-1)。
组分(B)：基础树脂
如本文中总结的实施例所示例的，组分(B)可以是基础树脂。所述基础树脂可以是线性聚乙烯。在这些实施例中，所使用的LLDPE-1为线性低密度聚乙烯PETROTHENE® GA602050。GA602050是粒状的为己烯共聚物线性低密度聚乙烯（密度：0.917 g/cm3；熔体指数，MI2: 2.0 g/10 min）。
组分(C)：添加剂
如本文中提供的实施例所示例的，组分(C)可以是一种或多种添加剂。例如，将IRGANOX® 1076和IRGAFOS® 168用作抗氧化剂。IRGANOX® 1010为可从CIBA获得的空间位阻酚抗氧化剂。IRGAFOS® 168是也可从CIBA获得的三芳基亚磷酸酯加工稳定剂。
实施例1：连接层1
源自组合物(A-1)[HDPE/EPR]的连接层粘合剂：
在200-240℃和210-250 rpm下，将粒状的接枝[HDPE/EPR]组合物(A-1)以20重量%与Irganox 1010抗氧化剂(0.1重量%)、Irgafos 168抗氧化剂(0.1重量%)和LLDPE-1 (平衡至100重量%)在挤出机中熔融共混以制备连接层粘合剂。可以将这种组合物称作连接层1。
作为对比的连接层2
源自接枝的HDPE、EPR和LLDPE的共混物的连接层粘合剂：
将接枝-1(13重量%)与Irganox 1010 (0.1重量%)、Irgafos 168 (0.1重量%)、LLDPE-1的粒料和EPR-1的粒料(7重量%)共混，其中接枝-1不再为活性聚合物。因此，在共混之前，已经使非活性的接枝-1淬灭或反应掉并整理成最终形式。在挤出机中熔化并混合干燥混合物（200-240℃, 210-250 rpm）。
下文的表1示出了连接层1和作为对比的连接层2的组成：
如可以看出的，连接层1和作为对比的连接层2之间的显著区别是，在连接层1的形成过程中，组分活性接枝-1和EPR-1在与LLDPE-1基础树脂结合之前反应到一起。在作为对比的连接层2中，接枝-1和EPR-1与LLDPE-1和其他组分共混到一起。
通过使用Killion挤出机，将连接层组合物成型为6密尔的膜材。
金属粘合性
然后测试连接层1和作为对比的连接层2的金属粘合性。为了进行对比，使用铝(Reynolds al 3001)作为金属基材来进行模拟的环剥离测试。在这个测试中，将连接层1和作为对比的连接层2切成5”×2”的条带，并夹在5.5”×2”的铝条带之间，预热至420oF并以1-2吨压制5分钟。然后，将压力升至20吨，持续30秒。然后，在20吨的压力下，将所述条带冷却至室温。然后将1 cm宽的样品切割并制成环，该环围绕与低位Instron柄连接的轴。然后在90℃的温度下，以50 mm/min剥离连接层组装件。结果示于图1中，其中连接层1的粘合性为157 N/10mm，而作为对比的连接层2的粘合性为105 N/10mm。
因此，出乎意料地，包含活性接枝聚烯烃与烯烃弹性体的反应产物的连接层组合物产生了比常规连接层粘合剂更优越的与金属的结合。

Claims (16)

1.多层结构，其包含：
金属基材，和
结合至所述金属基材的粘合剂组合物，所述组合物包含接枝组合物，且该接枝组合物包含活性接枝聚烯烃与烯烃弹性体的反应产物，
其中所述烯烃弹性体为乙丙橡胶(EPR)或三元乙丙橡胶(EPDM)，并且以所制备的接枝组合物的量计，所述烯烃弹性体的用量在30-40重量%的范围内。
2.根据权利要求1所述的多层结构，其中所述金属基材为包含铝、锡、锌、镍、铜、铂、金、银、钯、铬、钴、钢或铁及它们的混合物的金属、金属氧化物或合金。
3.根据权利要求1所述的多层结构，其中所述金属基材为金属箔层或管材。
4.根据权利要求1所述的多层结构，其中所述接枝聚烯烃为采用马来酸酐接枝的高密度聚乙烯(HDPE)。
5.根据权利要求1所述的多层结构，其中所述粘合剂组合物包含5-30重量%的接枝组合物和70-95重量%的基础树脂。
6.根据权利要求1所述的多层结构，其中所述接枝组合物包含马来酸酐接枝的聚乙烯与烯烃弹性体的反应产物，且所述粘合剂组合物还包含基础树脂，该基础树脂包含LLDPE。
7.层合材料，其包含：
金属基材，和
结合至所述金属基材的粘合剂组合物，所述组合物包含接枝组合物，且该接枝组合物包含活性接枝聚烯烃与烯烃弹性体的反应产物，
其中所述烯烃弹性体为乙丙橡胶(EPR)或三元乙丙橡胶(EPDM)，并且以所制备的接枝组合物的量计，所述烯烃弹性体的用量在30-40重量%的范围内。
8.根据权利要求7所述的层合材料，其中所述金属基材为包含铝、锡、锌、镍、铜、铂、金、银、钯、铬、钴、钢或铁及它们的混合物的金属、金属氧化物或合金。
9.根据权利要求7所述的层合材料，其中所述金属基材为金属箔层。
10.根据权利要求7所述的层合材料，其中所述接枝聚烯烃为用马来酸酐接枝的高密度聚乙烯(HDPE)。
11.根据权利要求7所述的层合材料，其中所述粘合剂组合物包含5-30重量%的接枝组合物和70-95重量%的基础树脂。
12.根据权利要求7所述的层合材料，其中所述接枝组合物包含马来酸酐接枝的聚乙烯与烯烃弹性体的反应产物，且所述粘合剂组合物还包含基础树脂，该基础树脂包含LLDPE。
13.用于制备多层结构的方法，其包括：
通过使活性接枝聚烯烃与烯烃弹性体反应来制备包含接枝组合物的粘合剂连接层组合物，以及
将所述粘合剂连接层组合物结合至金属基材，
其中所述烯烃弹性体为乙丙橡胶(EPR)或三元乙丙橡胶(EPDM)，并且以所制备的接枝组合物的量计，所述烯烃弹性体的用量在30-40重量%的范围内。
14.根据权利要求13所述的方法，其中所述金属基材为包含铝、锡、锌、镍、铜、铂、金、银、钯、铬、钴、钢或铁及它们的混合物的金属、金属氧化物或合金。
15.根据权利要求13所述的方法，其中所述接枝聚烯烃为用马来酸酐接枝的高密度聚乙烯(HDPE)。
16.根据权利要求13所述的方法，其中所述粘合剂连接层组合物还粘附至聚烯烃层。
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US10266727B2 (en) 2019-04-23
CN103118872A (zh) 2013-05-22
US20130260064A1 (en) 2013-10-03
EP2621724B1 (en) 2016-09-21
ES2601008T3 (es) 2017-02-13
EP2621724A1 (en) 2013-08-07
EP2621723B1 (en) 2016-10-26
CN103124638A (zh) 2013-05-29
WO2012044776A1 (en) 2012-04-05
US8637159B2 (en) 2014-01-28
CN103118872B (zh) 2016-04-13
EP2621723A1 (en) 2013-08-07
WO2012044768A1 (en) 2012-04-05
ES2594348T3 (es) 2016-12-19
US20120077048A1 (en) 2012-03-29

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