CN1568356A - 室温下可固化的x－hnbr涂层 - Google Patents

室温下可固化的x－hnbr涂层 Download PDF

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CN1568356A
CN1568356A CNA028199707A CN02819970A CN1568356A CN 1568356 A CN1568356 A CN 1568356A CN A028199707 A CNA028199707 A CN A028199707A CN 02819970 A CN02819970 A CN 02819970A CN 1568356 A CN1568356 A CN 1568356A
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coating composition
vulcabond
isocyanic acid
coating
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詹姆斯·R·哈拉戴
弗兰克·J·克拉科夫斯基
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Abstract

本发明公开了弹性体涂层组合物，所述组合物在室温下固化，并在弹性体上形成高度耐挠曲的、持久的和柔性的保护层，并提供了对弹性体基材和金属基材的良好粘合。涂层为(A)羧化氢化丙烯腈－丁二烯共聚物和(B)室温下的异氰酸酯固化组分的溶剂溶液。无需另外施加热量来固化涂层就可得到被涂敷的粘合的弹性体－金属复合材料。

Description

室温下可固化的X-HNBR涂层
发明领域
本发明涉及在弹性体上的保护性涂层。
发明背景
弹性体材料用于许多工业领域中。例如，弹性体材料用于制造各种软管、密封垫、台座、缓冲装置和绝缘装置，可在汽车和其它运载工具的发动机舱中找到。另外，在这些运载工具内用于安装发动机的装置典型地包括一个或多个金属部件，所述金属部件与一个或多个硫化弹性体部件粘着结合。在这些和许多其它利用硫化弹性体材料的工业领域中，弹性体材料典型地接触腐蚀性和降解性材料，如各种溶剂、油和燃料。当弹性体材料接触这些类型的材料时，弹性体材料具有降解的倾向，并在弹性体行业内一直在寻求制备耐腐蚀性材料的弹性体。
使弹性体材料成为耐腐蚀性材料的一种方法是给弹性体材料施用保护性涂层。以前用于柔性基材(例如，弹性体基材)和刚性基材(例如，钢、不锈钢、铝或塑料)的各种耐腐蚀的涂层包括聚氨酯、聚硫化物和氟碳弹性体。已发现，当常规耐腐蚀的涂层如氟碳弹性体施用到刚性基材上时，它们可提供优良的耐油和耐燃料的性质。然而，当应用到柔性的弹性体基材如天然橡胶或聚丁二烯时，氟碳弹性体具有差的耐疲劳性、差的低温性质、和差的与天然橡胶或聚丁二烯基材粘合的性质。
美国专利4,774,288公开了一种由共轭二烯和α，β-不饱和腈形成的氢化共聚物，其含有活性苯酚-甲醛树脂硫化系统。该公开文献涉及本体硫化橡胶，其特征在于具有良好的压缩应变性和良好的耐油性，以及在氧化环境下，在高温老化时良好的抗氧化攻击性，但是没有暗示具有溶剂的涂层可在柔性的弹性体基材如天然橡胶和聚丁二烯上形成，而这可能提供有用的性质。
美国专利5,314,955公开了一种涂层组合物，其由以下物质组成：(a)氢化的丙烯腈-丁二烯共聚物、(b)酚醛树脂、(c)固化组分、和(d)溶剂。该涂层解决了许多与具有耐疲劳性和耐燃料性的橡胶基材粘合所产生的问题。该涂层组合物的一个缺陷是，它要求高温烘烤来固化涂层并促进与相邻金属表面的粘合。一些部件如直升机转子轴承由于高温烘烤而遭损坏。高温烘烤的生产成本也是很高的，因为它增加了时间延迟和部件的附加处理。仍需要改善的保护性涂层以用于柔性的弹性体基材如天然橡胶和聚丁二烯，它们能耐疲劳和温度变化，从而对基材产生有效的粘合，并在室温下固化。
发明概述
本发明的涂层组合物能抗疲劳和温度变化，并提供与柔性的弹性体基材的良好粘合，并可在室温下固化。更具体地，本发明的涂层组合物包括：(A)一种羧化氢化丙烯腈-丁二烯共聚物(X-HNBR)；(B)一种固化组分，其包含至少一种异氰酸酯基团和一种形成交联键的基团；和(C)一种溶剂。在另一方面，提供了一种涂敷基材的方法，所述方法包括将上述基于溶剂的涂层施用到与金属粘合的硫化橡胶基材的表面，干燥涂层，使干燥后的涂层在环境条件下固化，任选地进行加热。优选地，还在弹性体周围所接触的部分金属上提供涂层。本发明提供了用于弹性体-金属复合材料的涂层，其在宽的温度范围内与弹性体基材具有良好的粘合，能耐腐蚀性材料，和抗挠曲疲劳。
发明详述
(A)X-HNBR
为了使烯键式不饱和腈-共轭二烯橡胶具有高饱和度，进行羧化腈丁二烯橡胶的氢化。氢化用于使橡胶的不饱和键中的至少80饱和。当饱和度小于80％时，橡胶的耐热性低，当饱和度高于优选值99％时，通过压缩应变等显示的橡胶弹性体下降过多。更优选的橡胶的饱和度为90-98％。
可用于制备羧化丙烯腈-丁二烯共聚物(该共聚物被进一步氢化)的共轭二烯可以是已知的共轭二烯中的任意一种，包括1，3-丁二烯、2-甲基-1，3-丁二烯、2，3-二甲基-1，3-丁二烯、1，3-戊二烯、1，3-己二烯、2，4-己二烯、1，3-庚二烯、戊间二烯和异戊二烯；本发明优选1，3-丁二烯，。
存在于X-HNBR中的羧基来自具有3至5个碳原子的α，β-不饱和一元羧酸，如丙烯酸、甲基丙烯酸和巴豆酸；和/或其它已知的包含羧基的单体，如但不限于具有4至5个碳原子的α，β-不饱和二元羧酸，例如马来酸、富马酸、柠康酸和衣康酸。所结合的不饱和羧酸的存在量按共聚物计为约1至约10重量百分比，这个量代替相应的共轭二烯的量。
另外，任选的第三单体可用于制备聚合物。优选地，第三单体为不饱和的一元或二元羧酸衍生物(例如，酯、酰胺等)。
不饱和腈共聚单体共聚化形成羧化丙烯腈-二烯共聚物，其典型地具有下式：
其中每个A为氢或具有1至约10个碳原子的烃基。A基团的实例包括烷基和环烷基，如甲基、乙基、异丙基、叔丁基、辛基、癸基、环戊基、环己基等；和芳基如苯基、甲苯基、二甲苯基、乙基苯基、叔丁基苯基等。丙烯腈和甲基丙烯腈是本发明优选的不饱和腈。
利用本领域的技术人员已知的方法，在存在自由基引发剂的情况下，通过上述任一示例的共轭二烯、不饱和腈和不饱和的包含羧基的共聚单体的反应可将X-HNBR共聚物加以聚合。适合的自由基引发剂不在本文范围之内，典型地为有机氧化物、过氧化物、氢过氧化物和偶氮化合物等，如过氧化氢、过氧化苯甲酰、氢过氧化枯烯、二-叔丁基过氧化物、驱蛔脑、过氧化乙酰、过氧化叔丁酰、三甲胺氧化物、二甲基苯胺氧化物、异丙基过氧化二碳酸酯、二异丁烯臭氧化物、过乙酸、硝酸盐、氯酸盐、高氯酸盐、偶氮二异丁腈等。
优选的市售X-HNBR由羧化腈-二烯共聚物经过两个步骤的氢化而制得。已知在NBR中，1，2-乙烯基-构型的丁二烯单元的C-C双键被快速氢化，然后1，4-顺式构型的单元的C-C双键被快速氢化。1，4-反式构型的丁二烯单元比较缓慢地被氢化。用于氢化的NBR产物的区别为占主要比例的1，4-反式构型的双键。
在2阶段氢化中，碳-碳双键首先被还原，然后还原碳-氮键。如本领域中已知的，这个步骤避免氢化聚合物的胶凝，如果在一个步骤中进行还原，就可能发生胶凝。在第一步中，使用不同的催化剂，例如钯或钌催化剂。但是，如果需要，通过适当选择催化剂可以只还原腈基，在聚合直链中留下不饱和的碳-碳键。也可以使用贵金属和镍或钴的组合，首先在较低温度下操作，然后在较高温度下操作。氢化丙烯腈-丁二烯共聚物的其它技术公开于例如美国专利4,581,417、4,631,315、和4,795,788；其公开内容引入本文以供参考。
最优选的丙烯腈-丁二烯共聚物典型地被氢化至一定程度，以使最终产物的不饱和度为约1至20摩尔百分比、优选约3至约7摩尔百分比。
羧化氢化腈橡胶(下文称为“X-HNBR”)由Bayer制造，商品名为“Therban”，例如Therban KA 8889。X-HNBR的碘值优选为约50％或更少，更优选约3％至40％、最优选约8％至30％。当使用碘值为50％或更少(高氢化比)的X-HNBR时，耐热和所需溶剂可得以增加，在低温下，通过使用具有低氢化比的X-HNBR橡胶，可保持橡胶弹性体。HNBR的腈含量的中心值优选为约15％至60％、更优选约30％至55％、最优选约40％至50％。通过使用腈含量为约15％或更多、尤其是约30％或更多的HNBR，耐溶剂性可得以增加；以及通过使用腈含量为约60％或更少、尤其是约50％或更少的橡胶，可保持抗低温性。另外，作为ML1+4的中心值(100℃)，它的门尼粘度(下文称为“门尼粘度”)优选为约40至100，对于涂层，优选较低的门尼粘度40-60。当使用门尼粘度落入这个范围内的X-HNBR时，涂层组合物具有高的耐有机液体性和良好的耐挠曲性和耐低温性。
(B)固化组分
固化组分包含至少一种异氰酸酯基团和一种与X-HNBR形成交联键的基团。优选的固化组分包含至少一种异氰酸酯基团或一种具有异氰酸酯基的基团、和羧基反应性交联基团。固化组分的最佳使用量按100重量份由共轭二烯、不饱和腈和羧基单体组成的所述羧化氢化共聚物计为3至30重量份。
能在低温下固化的示例类型的固化组分为二异氰酸酯和聚异氰酸酯，其包括脂族、环脂族和芳族异氰酸酯官能化合物。芳族聚异氰酸酯是优选的。二异氰酸酯或聚异氰酸酯的具体实例包括但不限于脂族聚异氰酸酯如1，6-六亚甲基二异氰酸酯；1，8-八亚甲基二异氰酸酯；1，12-十二亚甲基二异氰酸酯；2，2，4-三甲基六亚甲基二异氰酸酯等；3，3′-二异氰酸二丙醚；3-异氰酸甲基-3，5，5′-三甲基环己基(dexyl/hexyl？)异氰酸酯；六亚甲基二异氰酸酯；4，4′-亚甲基双(环己基异氰酸酯)；亚环戊基(cyclopentalene)-1，3-二异氰酸酯；亚环己基(cyclodexylene)-1，4，-二异氰酸酯；甲基2，6-二异氰酸caprolate；双-(2-异氰酸乙基)-富马酸酯；4-甲基-1，3-二异氰酸环己烷；反式-亚乙烯基二异氰酸酯和类似的不饱和聚异氰酸酯；4，4′-亚甲基-双(环己基异氰酸酯)和相关的聚异氰酸酯；甲烷二异氰酸酯；双-(2-异氰酸乙基)碳酸酯和类似的聚异氰酸碳酸酯；N，N′，N″-三-(6-异氰酸六亚甲基)缩二脲和相关的聚异氰酸酯。芳族二异氰酸酯和聚异氰酸酯包括甲苯二异氰酸酯；二甲苯二异氰酸酯；联茴香胺二异氰酸酯；4，4′-二苯基甲烷二异氰酸酯；1-乙氧基-2，4-二异氰酸苯；1-氯-2，4-二异氰酸苯；双(4-异氰酸苯基)甲烷；三(4-异氰酸苯基)甲烷；萘二异氰酸酯；4，4′-联苯基二异氰酸酯；亚苯基二异氰酸酯如m-和p-亚苯基二异氰酸酯；3，3′-二甲基-4，4′-联苯二异氰酸酯；p-异氰酸苯甲酰基异氰酸酯；四氯-1，3-亚苯基二异氰酸酯；2，4-甲苯二异氰酸酯，2，6-甲苯二异氰酸酯，4，4′-异氰酸酯，双-[异氰酸苯基]甲烷聚亚甲基聚(苯基异氰酸酯)，异佛乐酮(isophrone)二异氰酸酯和其它脂族、杂环和芳族聚异氰酸酯，并包括这些聚异氰酸酯的混合物。
提到的可用的二异氰酸酯的具体实例有1，6-己烷二异氰酸酯(市售的有例如商品名HMDI，得自Bayer)、异佛乐酮二异氰酸酯(市售的有例如商品名IPDI，得自Huls)、四甲基二甲苯二异氰酸酯(市售的有例如商品名m-TMXDI，得自Cytec)、2-甲基-1，5-戊烷二异氰酸酯、2，2，4-三甲基-1，6-己烷二异氰酸酯、1，12-十二烷二异氰酸酯和亚甲基双(4-环己基异氰酸酯)(市售的有例如DesmodurW，得自Bayer)、和较高官能度的异氰酸酯，如1，6-己烷二异氰酸酯的缩二脲(市售的有例如DesmodurN，得自Bayer)、1，6-己烷二异氰酸酯的异氰脲酸酯(市售的有例如DesmodurN-3390，得自Bayer)、异佛乐酮二异氰酸酯的异氰脲酸酯(市售的有例如DesmodurZ-4370，得自Bayer)、四甲基二甲苯二异氰酸酯和三羟甲基丙烷的反应产物(市售的有例如Cythane3160，得自Cytec)、和1摩尔的三羟甲基丙烷和3摩尔的甲苯二异氰酸酯的反应产物(市售的有例如DesmodurL，得自Bayer)。所包括的二异氰酸酯或聚异氰酸酯的量为3至30phr。所述量优选为8至15phr。
另一类固化组分为各种已知的有机硅烷，其包含一种异氰酸酯基团和另一种能够形成交联键的基团，如可水解基团，即卤素、羟基、烷氧基、或酰氧基；包含环氧基的基团；巯基；包含巯基的基团；乙烯基；包含乙烯基的基团；另一种异氰酸酯基团；包含另一种异氰酸酯的基团；脲基；包含脲基的基团；咪唑基团；或包含咪唑的基团。这些化合物是本领域已知的。
优选的与异氰酸硅烷形成交联键的基团为烷氧基。适合本发明的市售异氰酸-烷氧基硅烷的实例包括γ-异氰酸丙基三甲氧基硅烷，以商品名SilquestY-5187购自一Witco公司OSi Specialties Group(OSi)、和γ-异氰酸丙基三乙氧基硅烷，商品名SilquestA-1310，也得自OSi。
(C)溶剂
可用作本发明涂层组合物的载体赋形剂的溶剂可以基本上为任意的有机溶剂或其它已知溶解丙烯腈-丁二烯共聚物的物质。可用于本发明的有机溶剂的实例包括酮，如甲基乙基酮、甲基异丁基酮和二异丁基酮；乙酸酯，如乙酸丁酯；甲苯、二甲苯和它们的衍生物；硝基丙烷；和二氯化乙烯。
本发明溶剂的用量按总涂层组合物的重量计典型地为70％至97％、优选80％至90％，以使涂层组合物的总非挥发性固体含量为约3％至30％、优选约6％至15％。
本发明的涂层组合物可包含其它任选成分，如金属氧化物、抗氧化剂和颗粒增强物如炭黑和颜料如TiO2。金属氧化物的具体实例包括氧化锌、氧化镁、硫酸锌和氧化铅，而用于本发明的颗粒增强物的具体实例包括炭黑、沉淀二氧化硅和热解法二氧化硅。任选的颗粒增强物的各种用量按羧化氢化丙烯腈-丁二烯共聚物的重量计可高至约50％。
可通过刮刀等用手简单地混合成为或通过机械混合或振荡成分，从而制得涂层组合物。通过浸渍、喷射、擦拭、刷洗等，涂层组合物典型地被施用到弹性体材料和/或其它基材，然后将涂层干燥一段时间，典型地为约30分钟至2小时、优选约45分钟至1小时。涂层组合物典型地被施用到基材上形成干燥层，其厚度为0.1至5密耳、优选约0.5至1.5密耳。
在室温下，涂层组合物将在约2至24小时内固化。通过将涂层暴露在高温下可加速固化，但这不是必需的。
基材
本发明涂层组合物特别适用于涂敷发动机架装置，所述装置包括已粘合到金属部件的硫化弹性体部件。组合物在具有有限的耐油和耐溶剂的硫化弹性体上是特别有效的涂层。这些弹性体包括天然橡胶、苯乙烯丁二烯橡胶、聚丁二烯橡胶、乙烯丙烯和乙烯丙烯二烯橡胶、聚异丁烯-异戊二烯橡胶、聚氯丁二烯、低丙烯腈含量(＜35％)的腈-丁二烯橡胶等。涂层组合物也可用在刚性基材上，所述刚性基材如金属、塑料、陶瓷和复合材料。这对于粘合橡胶架是特别有用的，所述橡胶架包含弹性体和刚性组件。
制备用于涂敷的弹性体基材
待涂敷的弹性体表面或基材可任选地用氯化剂如次氯酸钠和盐酸预处理。使用不同的氯化剂来制备弹性体材料以施用涂层组合物，这是本领域熟知的。氯化剂的一个实例市售自Lord Corporation，商品名为CHEMLOK 7701。氯化剂可通过刷洗、浸渍、喷射、擦拭等施用到弹性体材料的表面，然后使氯化剂变干。氯化剂倾向于极易于挥发，典型地在几秒或几分钟内变干。
本发明的涂层组合物令人惊奇地能够充分粘合柔性的弹性体部件和刚性的金属部件，使得弹性体和金属之间的界面能被涂层组合物充分保护。因此本发明不同于许多常规保护性涂层组合物，它们仅能粘合一类待保护的基材。
下列实施例用于说明本发明，不应理解为限制由权利要求书限定的本发明的范围。
实施例1
使用Zetpol 2220，这是由Zeon Chemical制备的一种X-HNBR，由此制备下面的实施例。适合的取代物是TherbanKA 8889。
弹性体涂层溶液按下述方法制备：
成分      描述                   PHR
X-HNBR    羧化氢化腈-丁二烯      100.0
将该制剂溶于甲基异丁基酮(MIBK，CAS No.108-10-1)至固体含量按重量计为12.0％。
向40克53％二甲苯溶液中，以0.1g、0.5g和1.0g水平加入双-[异氰酸苯基]甲烷(二异氰酸酯)。在0.1g二异氰酸酯水平，溶液在室温下在小于16小时内固化。在0.5g水平，溶液在30分钟内固化。
向40克溶液中，以0.3、0.7、1.0和1.3克量加入3-异氰酸丙基三乙氧硅烷，CAS#24801-88-5。在所有的水平中，涂层组合物在45分钟至1小时内开始固化，并在小于16小时内完全固化。
耐燃料测试
将涂层在硬度为55的天然橡胶化合物(A135Q)上测试。所述化合物已用Chemlok7701处理。然后将涂层与市售氟碳涂层PLV-2100、美国专利5,314,955所教导的市售HNBR SPE XV涂层、和未涂敷的对照物比较。
当在室温下在Jet A燃料中浸渍24小时后，得到下列溶涨体积百分比结果：
未涂层对照物                             192.9％
对照的PLV 2100                               0.1％
对照的HNBR SPE XV                            33.6％
具有双-[异氰酸苯基]甲烷的实施例涂层          2.2％
具有3-异氰酸丙基三乙氧硅烷的实施例涂层       2.3％
粘合力测试
通过将两个一英寸宽的带子粘合在一起，并以180°剥力(peel)来拉动，从而测试橡胶粘合性。由硬度为55的市售天然橡胶化合物(A135Q)来制备橡胶带，所述化合物已用Chemlok7701处理。涂敷约两英寸长的部分，将各个带彼此接触放置，并施加472g重量来保证紧密接触。将重物保留在位十分钟。在8天的干燥时间后，将各个带用Tinius Olsen张力检验器分开。下表记录了这些结果。
涂层类型                                  剥离结果，Lbf
对照的PLV 2100                            2.03
对照的HNBR SPE XV                         8.52
具有双-[异氰酸苯基]甲烷的实施例涂层       15.5
具有3-异氰酸丙基三乙氧硅烷的实施例涂层    21.1
通过将一英寸宽的橡胶带粘合到一英寸的金属检查片(coupon)上，其中有一平方英寸相互重叠，以剪切力来测试金属粘合力。通过硬度为55的天然橡胶化合物(A135Q)来制备橡胶带，所述化合物已用Chemlok7701处理过。金属检查片为304不锈钢。选择不锈钢是因为已知它是一种难以粘合的基材。在涂层后，将各个带彼此接触放置，并施加472g重量来保证紧密接触。将重物保留在位十分钟。在8天的干燥时间后，将各个样品用Tinius Olsen张力检验器分开。
涂层类型                                  粘合力结果，psi
对照的PLV 2100                            16.78
对照的HNBR SPE XV                         19.23
具有双-[异氰酸苯基]甲烷的实施例涂层     18.2
具有3-异氰酸丙基三乙氧硅烷的实施例涂层  18.5
耐臭氧性
使用动态臭氧测试(ASTM-D3395)，在50pphm的臭氧浓度下，在104°F进行臭氧测试。
样品基于硬度为55的市售硫化天然橡胶/聚丁二烯掺合物，所述掺合物用抗臭氧蜡和烷基芳基亚苯基-二胺抗臭氧剂(M122N)来保护。在动态条件下，看起来羧化氢化涂层作为臭氧屏障比HNBR涂层SPEXV更有效。
引发的裂解
未涂层的对照物                     6.5小时
对照的HNBR SPE XV                  6.5小时
具有双-[异氰酸苯基]甲烷的实施例1涂层在28小时未裂解。
具有3-异氰酸丙基三乙氧硅烷的实施例1涂层在28小时未裂解。
除了具有低的粘合值外，在挠曲后，PLV 2100涂层裂解了，并从橡胶表面剥离。未刺穿的DeMattia挠曲样品(由硬度为55的天然橡胶化合物制备)涂以这些相同的涂层，并根据ASTM D-813弯曲。PLV-2100涂层发生严重裂解并脱落，在小于4000转内暴露基材。烘烤的HNBR SPE XV和实施例1运行了80,000转，此时天然橡胶基材开始裂解。在这些实施例涂层中没有脱落迹象。

Claims (19)

1.一种基于溶剂的涂层组合物，所述组合物包括3至30重量百分比的固体，所述固体包括：(a)一种包含由共轭二烯、不饱和腈和羧基单体组成的重复单元的羧化氢化共聚物；(b)一种包含至少一种异氰酸酯基团和另一种形成交联键的基团的固化组分；和(C)一种溶剂。
2.如权利要求1所述的涂层组合物，其中所述共轭二烯选自1，3-丁二烯；2，3-二甲基丁二烯；1，3-戊二烯；1，3-己二烯；2，4-己二烯；1，3-庚二烯；戊间二烯和异戊二烯。
3.如权利要求2所述的涂层组合物，其中所述共轭二烯为1，3-丁二烯。
4.如权利要求1所述的涂层组合物，其中所述不饱和腈具有下式：
Figure A028199700002C1
其中各个A为氢或具有1至约10个碳原子的烃基。
5.如权利要求1所述的涂层组合物，其中所述不饱和腈为丙烯腈或甲基丙烯腈。
6.如权利要求1所述的涂层组合物，其中所述羧化氢化共聚物的不饱和度为约0.1至20摩尔百分比。
7.如权利要求6所述的涂层组合物，其中不饱和度为约3至7摩尔百分比。
8.如权利要求1所述的涂层组合物，其中所述溶剂选自酮；乙酸酯；甲苯、二甲苯及其衍生物；硝基丙烷；和二氯化乙烯。
9.如权利要求1所述的涂层组合物，其中所述固化组分为二异氰酸酯或聚异氰酸酯。
10.如权利要求9所述的涂层组合物，其中所述二异氰酸酯或聚异氰酸酯选自1，6-六亚甲基二异氰酸酯；1，8-八亚甲基二异氰酸酯；1，12-十二亚甲基二异氰酸酯；2，2，4-三甲基六亚甲基二异氰酸酯等；3，3′-二异氰酸二丙醚；3-异氰酸甲基-3，5，5′-三甲基环己基异氰酸酯；六亚甲基二异氰酸酯；4，4′-亚甲基双(环己基异氰酸酯)；亚环戊基-1，3-二异氰酸酯；亚环己基-1，4，-二异氰酸酯；甲基2，6-二异氰酸caprolate；双-(2-异氰酸乙基)-富马酸酯；4-甲基-1，3-二异氰酸环己烷；反式-亚乙烯基二异氰酸酯；4，4′-亚甲基-双(环己基异氰酸酯)；甲烷二异氰酸酯；双-(2-异氰酸乙基)碳酸酯；N，N′，N″-三-(6-异氰酸六亚甲基)缩二脲；甲苯二异氰酸酯；二甲苯二异氰酸酯；联茴香胺二异氰酸酯；4，4′-二苯基甲烷二异氰酸酯；1-乙氧基-2，4-二异氰酸苯；1-氯-2，4-二异氰酸苯；双(4-异氰酸苯基)甲烷；三(4-异氰酸苯基)甲烷；萘二异氰酸酯；4，4′-联苯基二异氰酸酯；m-亚苯基二异氰酸酯；p-亚苯基二异氰酸酯；3，3′-二甲基-4，4′-联苯基二异氰酸酯；p-异氰酸苯甲酰基异氰酸酯；四氯-1，3-亚苯基二异氰酸酯；2，4-甲苯二异氰酸酯，2，6-甲苯二异氰酸酯，4，4′-异氰酸酯，双-[异氰酸苯基]甲烷聚亚甲基聚(苯基异氰酸酯)，异佛乐酮二异氰酸酯，及其混合物。
11.如权利要求9所述的涂层，其中所述二异氰酸酯或聚异氰酸酯的含量按100重量份由共轭二烯、不饱和腈和羧基单体组成的所述羧化氢化共聚物计为3至30重量份。
12.如权利要求10所述的涂层，其中所述二异氰酸酯或聚异氰酸酯的含量按100重量份由共轭二烯、不饱和腈和羧基单体组成的所述羧化氢化共聚物计为8至15重量份。
13.如权利要求1所述的涂层组合物，其中所述固化组分为包含异氰酸酯基团和另一个能形成交联键的基团的有机硅烷。
14.如权利要求12所述的涂层组合物，其中所述可水解基团选自卤素、羟基、烷氧基和酰氧基。
15.如权利要求13所述的涂层组合物，其中所述能形成交联键的基团选自具有环氧基的基团、巯基、具有巯基的基团、乙烯基、具有乙烯基的基团、另一种异氰酸酯基团、具有异氰酸酯基的基团、脲基、具有脲基的基团、咪唑基、以及具有咪唑基的基团。
16.如权利要求13所述的涂层组合物，其中所述有机硅烷为异氰酸-烷氧基硅烷。
17.如权利要求16所述的涂层组合物，其中所述异氰酸酯-烷氧基硅烷为γ-异氰酸丙基三甲氧硅烷或γ-异氰酸丙基三乙氧硅烷。
18.一种涂敷基材的方法，所述方法包括将权利要求1的基于溶剂的涂层组合物施用到与金属粘合的硫化橡胶基材的表面，干燥涂层，并使所述干燥后的涂层在环境条件下固化，任选地进行加热。
19.一种由金属粘合柔性弹性体组成的粘合复合材料，所述复合材料被涂敷到所述弹性体的整个表面上，并至少部分涂敷到靠近弹性体周围的所述金属上，所述涂层由溶剂溶液的干燥残余物形成，所述溶剂溶液包括：(a)一种包含由共轭二烯、不饱和腈和羧基单体组成的重复单元的羧化氢化共聚物；(b)一种包含至少一种异氰酸酯基团和另一种形成交联键的基团的固化组分；和(C)一种溶剂。
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