CN101027374B - 衍生自官能化的乙烯共聚物的粘合剂组合物 - Google Patents

衍生自官能化的乙烯共聚物的粘合剂组合物 Download PDF

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CN101027374B
CN101027374B CN2005800252514A CN200580025251A CN101027374B CN 101027374 B CN101027374 B CN 101027374B CN 2005800252514 A CN2005800252514 A CN 2005800252514A CN 200580025251 A CN200580025251 A CN 200580025251A CN 101027374 B CN101027374 B CN 101027374B
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ethylene
weight
multipolymer
copolymer
composition
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CN101027374A (zh
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R.T.周
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Dow Chemical Co
Dow Global Technologies LLC
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EI Du Pont de Nemours and Co
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Abstract

本发明公开了包含非官能化的基础树脂和直接在高压的高压釜中合成的官能化乙烯共聚物(如乙烯/马来酸酐(E/MAH)或乙烯/马来酸单乙酯(E/MAME)共聚物)的粘合剂组合物。这些粘合剂组合物可作为自支承性膜施用或可共挤出或挤出涂布到基材上。本发明还公开了包含这些组合物的多层结构、膜、管道涂层和建筑物护墙板。

Description

衍生自官能化的乙烯共聚物的粘合剂组合物
本申请要求2004年7月29日提交的美国临时申请号60/592,213的权益。
                    发明背景
发明领域
本发明涉及粘合剂组合物。本发明也涉及包含粘合剂组合物的物品。
发明描述
经反应性基团官能化(通常通过马来酸酐接枝)的改性聚合物广泛用作挤出和层压粘合剂，特别是用作多层复合结构中的粘合剂层。马来酸酐接枝聚合物(常被称为“马来化”聚合物)也常用在管道涂层和建筑物护墙板中。
马来酸酐接枝聚合物包括马来化聚乙烯、马来化聚丙烯、马来化苯乙烯-乙烯-丁烯-苯乙烯三嵌段共聚物和马来化聚丁烯。乙烯/丙烯酸烷基酯/一氧化碳三元共聚物、乙烯/醋酸乙烯酯共聚物、乙丙橡胶也可经马来酸酐接枝改性。马来酸酐改性线形高密度聚乙烯的实例为Crompton公司以商标Polybond
Figure G05825251420070130D000011
3009出售的产品。类似的马来化聚烯烃可从DuPont以商标Fusabond
Figure G05825251420070130D000012
买到。
美国专利5,516,583、4,861,676、4,861,677、4,552,819和5,965,255公开了粘合剂组合物。美国专利5,225,482公开了包含乙烯-醋酸乙烯酯共聚物、苯乙烯聚合物树脂、接枝改性聚乙烯、聚苯乙烯弹性体和乙烯-烯烃共聚物的粘合剂组合物。PCT专利公布WO01/18141公开了包含聚烯烃、官能化聚烯烃、聚苯乙烯组合物和弹性体的粘合剂组合物。
常规的改性聚烯烃或者损失对金属或对聚烯烃的粘结强度，或者当与金属或聚烯烃粘结时不能在低温下活化。此外，在低温下活化的粘合剂组合物可能是非常软和粘的材料，以致在热层压工艺中这些组合物作为游离膜(free film)的加工可能比较麻烦并可能需要非常昂贵的离型膜以防止粘连。另外，在投入使用后，粘合剂可能随时间而显著失去其粘结强度。这个现象在工业中被称为“老化”。
马来化聚烯烃和其他马来酸酐接枝共聚物的生产和使用不是没有问题的。例如，在通过接枝得到的马来化聚烯烃中可能难以达到高度的官能化，原因是所需的反应条件可能引起不希望有的副反应，如交联和断链。为此，在高于约2％重量的浓度下进行的马来酸酐的接枝可能是困难并棘手的。
可能需要使用没有马来化聚烯烃中高度接枝所伴随的问题而能提供优越的粘合性能的粘合剂组合物。
含反应性官能团(如马来酸酐)的乙烯共聚物可用高压自由基工艺通过直接共聚容易地获得。这样的高压工艺见述于例如美国专利4,351,931。
PCT专利申请公开WO2003/099930 A1描述了经冲击改性剂组合物增韧的聚酰胺，所述冲击改性剂包含自乙烯和官能化共聚单体制得的共聚物，其中所述官能化共聚单体在共聚物中的含量在约3-约15％重量的范围内。
发明简述
一方面，本发明涉及改进的粘合剂共混组合物，所述组合物包含自高压的高压釜反应器得到的烯烃/马来酸酯共聚物并共混有非官能化的基础树脂。
另一方面，本发明涉及一种聚合物粘合剂组合物，所述粘合剂组合物包含：
(a)烯烃与约3％重量-约15％重量的官能化共聚单体的共聚物；和
(b)聚合物基础树脂；
其中所述粘合剂组合物包含约5-约50％重量的组分(a)和约50-约95％重量的组分(b)。
另一方面，本发明涉及一种粘合剂膜，所述粘合剂膜包含(a)烯烃与约3％重量-约15％重量的官能化共聚单体的共聚物；和
(b)聚合物基础树脂；
其中所述粘合剂组合物包含约5-约50％重量的组分(a)和约50-约95％重量的组分(b)。
另一方面，本发明涉及一种多层复合结构，所述多层复合结构包含(a)烯烃与约3％重量-约15％重量的官能化共聚单体的共聚物；和
(b)聚合物基础树脂；
其中所述粘合剂组合物包含约5-约50％重量的组分(a)和约50-约95％重量的组分(b)。
另一方面，本发明涉及一种物品，所述物品包含(a)烯烃与约3％重量-约15％重量的官能化共聚单体的共聚物；和
(b)聚合物基础树脂；
其中所述粘合剂组合物包含约5-约50％重量的组分(a)和约50-约95％重量的组分(b)。
发明详述
本文所公开的所有参考文献通过引用结合到本文中。
在一个实施方案中，本发明涉及改进的粘合剂共混组合物，所述组合物包含自高压的高压釜反应器得到的烯烃/马来酸酯共聚物并共混有非官能化的基础树脂。
术语“(甲基)丙烯酸”指甲基丙烯酸和/或丙烯酸。同样，术语“(甲基)丙烯酸酯”指甲基丙烯酸酯和/或丙烯酸酯。
就本发明的目的而言，聚烯烃为烯烃单体的均聚物和共聚物。更具体地讲，均聚物包括由单一的不饱和烯烃组成的聚合物，如聚乙烯、聚丙烯、聚丁烯或其中的烯烃含二到二十个碳原子的类似聚合物。烯烃的共聚物包括由一种或多种不饱和的或多重不饱和的、含二到二十个碳原子的烃组成的聚合物。实例包括但不限于乙烯/丙烯共聚物、乙烯/丁烯共聚物、乙烯/己烯共聚物、乙烯/辛烯共聚物、乙烯/苯乙烯共聚物、乙烯/丁烯/辛烯共聚物、乙烯/丙烯/降冰片二烯共聚物和丙烯/丁烯共聚物。
在本专利说明书中，术语“官能化共聚物”指烯烃(特别是乙烯)与具有特定的官能团的共聚单体的共聚物，所述特定的官能团能反应形成共价或离子键。
术语“接枝聚烯烃”指聚烯烃、非烯烃共聚物或聚烯烃和/或非烯烃共聚物的混合物或共混物，其上被接枝了至少一个选自烯属不饱和羧酸和烯属不饱和羧酸酸酐的单体，包括不那么优选的这类酸的衍生物及其混合物。所述酸和酸酐可为单-、二-或多羧酸，其实例为丙烯酸、甲基丙烯酸、马来酸、富马酸、衣康酸、巴豆酸、衣康酸酐、马来酸酐和取代的马来酸酐(如二甲基马来酸酐或citrotonic酸酐)、纳迪克(5-降冰片烯-2，3-二甲酸)酸酐、甲基纳迪克(甲基-5-降冰片烯-2，3-二甲酸)酸酐和四氢邻苯二甲酸酐，特别优选马来酸酐。所述不饱和酸的衍生物其实例为盐、酰胺、酰亚胺和酯，如马来酸单钠和二钠、丙烯酰胺、甲基丙烯酸缩水甘油酯和富马酸二甲酯。接枝聚烯烃在本领域内广为人知，可用多种方法生产，包括在挤出机或其他混合设备中热接枝、在溶液中接枝或在流化床反应器中接枝。接枝聚烯烃的共混物或混合物也可用。
在本专利说明书中，术语“聚苯乙烯类”或“聚苯乙烯”指苯乙烯或α-甲基苯乙烯的均聚物或苯乙烯与不饱和单体(如但不限于乙烯、丁烯、丁二烯或异戊二烯)的共聚物。具体实例包括但不限于乙烯/苯乙烯无规或嵌段共聚物、乙烯/丁二烯无规或嵌段共聚物和氢化及部分氢化的丁二烯/苯乙烯共聚物。经进一步改性以提高冲击性、常被称作高抗冲聚苯乙烯或HIPS的聚苯乙烯类也可用。聚苯乙烯类的共混物和混合物也可用。具体实例包括但不限于Nova Chemicals出售的高性能苯乙烯类和Dow Chemical以商品名IndexTM出售的乙烯/苯乙烯共聚物。
在本专利说明书中，术语“弹性体”也指聚烯烃或聚苯乙烯类，但其与上述之聚烯烃或聚苯乙烯类的区别在于其结晶度相当低，也就是说，呈相对无定形态。本文中定义的弹性体在10摄氏度/分钟的加热速率下的熔化热将低于30焦耳/克(用差示扫描量热法(DSC)测得)。聚烯烃弹性体可为例如乙烯与α-烯烃的共聚物，可包括ExxonMobil以商品名“Exact
Figure G05825251420070130D000051
”出售的低密度茂金属乙烯/丁烯共聚物或DuPont Dow Elastomers以商品名“Engage
Figure G05825251420070130D000052
”出售的茂金属乙烯/辛烯共聚物。聚烯烃弹性体也包括ExxonMobil以商品名“Vistalon
Figure G05825251420070130D000053
”出售的乙烯/丙烯共聚物、Mitsui以商品名“Tafmer”出售的乙烯/α-烯烃共聚物或DuPont Dow Elastomers以商品名“Nordel
Figure G05825251420070130D000055
”出售的乙烯/丙烯/降冰片二烯共聚物。聚烯烃弹性体也包括聚丁烯橡胶、聚异丁烯。聚苯乙烯类弹性体的实例包括例如Shell以商品名“Kraton
Figure G05825251420070130D000056
”出售的二嵌段和三嵌段共聚物或Firestone以商品名“Stereon
Figure G05825251420070130D000057
”出售的那些。
本发明的粘合剂组合物其各种组分优选赋予最终的粘合剂一定的特性。低熔点的基础树脂(如聚乙烯或乙烯/醋酸乙烯酯共聚物)能增强粘合剂的低温活化性。官能化的共聚物主要赋予粘合剂组合物对基材(例如更高极性的聚合物(如聚酰胺)或金属)的优良粘结。
官能化共聚物
本发明的粘合剂组合物包含自烯烃和官能化共聚单体制得的共聚物，更具体地讲，包含烯烃(特别是乙烯)与马来酸酐或其官能化等价物的共聚物。
本文中用到的术语“烯烃/马来酸酯共聚物”指自烯烃和官能化共聚单体(如马来酸酐或马来酸酐的官能化等价物)制得的共聚物。这样的等价物包括马来酸酐的衍生物如马来酸和/或其盐、马来酸二酯、马来酸单酯、衣康酸、富马酸、富马酸单酯、或任何这些的混合物。烯烃/马来酸酯共聚物也包括E/X/Y三元共聚物，其中：E为乙烯；X为选自醋酸乙烯酯、(甲基)丙烯酸和/或其衍生物的单体；Y为马来酸酐或其官能化等价物。适于用作组分X的单体的实例为(甲基)丙烯酸衍生物，包括酸、盐、酯、酸酐或化学领域内普通技术人员熟知的其他酸衍生物。丙烯酸甲酯和丙烯酸丁酯是适于用作组分X的丙烯酸酯单体的具体实例。适于用作Y组分的为马来酸酐、马来酸二酯或单酯(马来酸半酯)，包括C1-C4醇(如甲醇、乙醇、正丙醇、异丙醇和正丁醇)的酯。优选所述烯烃/马来酸酯共聚物含马来酸酐、马来酸二酯和/或马来酸半酯。更优选所述烯烃/马来酸酯共聚物含马来酸酐。也更优选所述烯烃/马来酸酯共聚物含马来酸半酯。
本发明中有用的烯烃/马来酸酯共聚物通过高压自由基聚合法获得。适用于本发明的实践中的高压法见述于例如美国专利4,351,931，其公开通过引用结合到本文中。
聚合物基础树脂
本发明的粘合剂组合物包含热塑性聚合物基础树脂作为第二种组分。组合物中使用的所述聚合物包括但不限于聚烯烃，如高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线形低密度聚乙烯(LLDPE)、超高分子量聚乙烯(UHMWPE)、超低密度聚乙烯(ULDPE)、茂金属聚乙烯(或MPE)(使用茂金属催化剂获得的乙烯与α-烯烃单体的共聚物)、乙烯/丙烯共聚物、三元共聚物如乙烯/丙烯/二烯单体三元共聚物(EPDM)和聚丙烯均聚物及共聚物。
适合的基础树脂也可包括自乙烯与极性单体共聚获得的乙烯共聚物。这类适合的共聚物包括乙烯/醋酸乙烯酯共聚物(EVA)和乙烯/(甲基)丙烯酸酯共聚物。乙烯/(甲基)丙烯酸酯共聚物包括乙烯/丙烯酸共聚物、乙烯/甲基丙烯酸共聚物、可从乙烯/丙烯酸和/或甲基丙烯酸共聚物衍生得到的盐、乙烯/丙烯酸酯共聚物、乙烯/甲基丙烯酸酯共聚物和/或任何这些的混合物。
适合的基础树脂也可包括聚氯乙烯、氯化聚氯乙烯和聚苯乙烯。
两种或多种聚合物的组合也可用。
为将两种聚合物材料粘结到一起(如将LDPE粘结到聚酰胺(尼龙)如尼龙6上)，优选所述基础树脂选自高密度聚乙烯、低密度聚乙烯、线形低密度聚乙烯、超高分子量聚乙烯、超低密度聚乙烯、使用茂金属催化剂获得的乙烯与α-烯烃单体的共聚物(茂金属聚乙烯)、乙烯/丙烯共聚物、三元共聚物如乙烯/丙烯/二烯单体三元共聚物、和聚丙烯均聚物及共聚物。更优选所述基础树脂为MPE、LDPE或LLDPE。特别优选LDPE。
尽管不希望受理论束缚，由于其基本为线形的结构以及PE的窄分子量分布，因此MPE也是本发明的实践中特别优选的。MPE技术能制得高柔性和低结晶度的低密度PE，其作为本发明的基础树脂组分可能是理想的。
MPE技术见述于例如美国专利5,272,236、美国专利5,278,272、美国专利5,507,475、美国专利5,264,405和美国专利5,240,894。
为粘结到金属基材如铝箔上，所述第二种组分基础树脂优选选自MPE、乙烯与醋酸乙烯酯的共聚物或乙烯与丙烯酸烷基酯的共聚物。
术语“乙烯/丙烯酸烷基酯共聚物”包括乙烯与丙烯酸烷基酯的共聚物，其中所述烷基部分含一到六个碳原子。丙烯酸烷基酯的实例包括丙烯酸甲酯、丙烯酸乙酯和丙烯酸丁酯。“乙烯/丙烯酸甲酯(缩写为EMA)”指乙烯(缩写为E)与丙烯酸甲酯(缩写为MA)的共聚物。“乙烯/丙烯酸乙酯(缩写为EEA)”指乙烯(缩写为E)与丙烯酸乙酯(缩写为EA)的共聚物。“乙烯/丙烯酸丁酯(缩写为EBA)”指乙烯(缩写为E)与丙烯酸丁酯(缩写为BA)的共聚物。值得一提的是自丙烯酸异丁酯共聚单体(EiBA)制得的乙烯/丙烯酸丁酯共聚物和自丙烯酸正丁酯共聚单体(EnBA)制得的乙烯/丙烯酸丁酯共聚物。
原则上，结合进乙烯/丙烯酸烷基酯共聚物中的丙烯酸烷基酯共聚单体的相对量可在占总的共聚物的少许几个重量百分数到高达40％重量的范围内宽泛地变化或甚至更高。与之类似，烷基的选择原则上可从简单甲基到有或没有显著支化的六碳原子烷基。丙烯酸烷基酯共聚单体中存在的烷基的相对量和选择可被看作是确定所得之乙烯共聚物如何以及至何种程度被看作热塑性组合物中的极性聚合物组分。
优选所述丙烯酸烷基酯共聚单体中的烷基有一到四个碳原子，且所述丙烯酸烷基酯共聚单体的含量范围为乙烯/丙烯酸烷基酯共聚物的5-30％重量，优选10-25％重量。
乙烯/丙烯酸烷基酯共聚物可用高压釜或管式反应器通过聚合物领域中众所周知的工艺制备。共聚合可在高压釜中以连续法进行：乙烯、丙烯酸烷基酯和任选溶剂如甲醇(参见美国专利5,028,674)连同引发剂被连续地加到美国专利2,897,183中所公开类型的搅拌着的高压釜中。加料速率取决于变量如聚合温度、压力、所用的丙烯酸烷基酯单体以及要获得所述共聚物的目标组合物所需的反应混合物中单体的浓度。在一些情况下，可能需要使用调聚剂如丙烷来控制分子量。反应混合物从高压釜中连续地移除。在反应混合物离开反应器后，通过常规的方法，如在升高的温度下减压蒸发未聚合的物料和溶剂，共聚物从未反应的单体和溶剂(如果用了溶剂的话)中分离出来。
正如本领域内普遍熟知的，管式反应器生产的乙烯/丙烯酸烷基酯共聚物不同于更常规的高压釜生产的乙烯/丙烯酸烷基酯。因此，就本发明的目的而言，术语“管式反应器生产的”乙烯/丙烯酸烷基酯共聚物表示在管式反应器等(其中，乙烯和丙烯酸烷基酯共聚单体各自不同的反应动力学固有的后果通过有意地沿管式反应器中的反应流程引入单体而得到减轻或部分补偿)中于高压和升高的温度下生产的乙烯共聚物。正如本领域内普遍公认的，这样的管式反应器共聚合法将产生沿聚合物骨架具有更高相对程度的非均匀性的共聚物(共聚物呈更不均匀的分布)，将会减少支化长链的存在，并将产生比在高压下搅拌着的高压釜反应器中相同共聚单体比率下所产生的共聚物具有更高熔点的共聚物。管式反应器生产的乙烯/丙烯酸烷基酯共聚物通常较高压釜生产的乙烯/丙烯酸烷基酯共聚物更硬且更有弹性。
这类管式反应器生产的具有上述特性的乙烯/丙烯酸烷基酯共聚物其商品可从E.I.du Pont de Nemours & Co.，Wilmington，Delaware买到。
前述管式反应器乙烯/丙烯酸烷基酯共聚物的实际生产优选在高压管式反应器中于升高的温度下进行，同时沿管另外加入反应物共聚单体而不是仅仅在搅拌着的高温高压的高压釜型反应器中生产。但应该理解，类似的乙烯/丙烯酸烷基酯共聚物可在一系列高压釜反应器中生产，其中共聚单体的更换(replacement)通过多区引入反应物共聚单体而实现，如美国专利3,350,372、3,756,996和5,532,066中的公开，因而，就本发明的目的而言，这些高熔点物质应认为是等价的。
为进一步说明和表征管式反应器生产的乙烯/丙烯酸烷基酯共聚物(相对于常规的高压釜生产的共聚物)，下表所列的商品乙烯/丙烯酸烷基酯共聚物及其熔点数据表明管式EMA树脂由于MA沿聚合物链的分布很不相同而具有大大高于高压釜EMA的熔点：
高压釜生产的共聚物
Figure G05825251420070130D000091
管式反应器生产的共聚物
EMA-T1(MA占25％重量)mp＝88℃|EMA-T2(MA占20％重量)mp＝95℃
关于管式反应器生产的和高压釜生产的乙烯/丙烯酸烷基酯共聚物的不同之处的其他讨论，请参阅Richard T.Chou，Mimi Y.Keatingand Lester J.Hughes，“High Flexibility EMA made from High PressureTubular Process(自高压管式工艺生产的高柔性EMA)”，AnnualTechnical Conference-Society of Plastics Engineers(2002)，60th(第2卷)，1832-1836。CODEN：ACPED4 ISSN：0272-5223；AN 2002：572809；CAPLUS。
适用于本发明的乙烯/丙烯酸烷基酯共聚物可从DuPont买到。关于可从DuPont买到的管式反应器生产的乙烯/丙烯酸烷基酯共聚物的具体实例，请参见表A。
表A
乙烯/丙烯酸烷基酯    丙烯酸烷基酯，％重    熔体流动指数
共聚物               量                    (g/10min)
EMA-1                25                    0.4
EMA-2                25                    0.6
EMA-3                9                     2
EMA-4                14                    2
EMA-5                18                    2
EMA-6                24                    2
EMA-7                9                     6
EMA-8                20                    8
EMA-9                13                    9
EEA-1                12                    1
EEA-2                16                    1
EEA-3                15                    6
EEA-4                15                    7
EBA-1                7                     1.1
EBA-2                7                     1.1
EBA-3                17                    1.5
EBA-4                17                    1.8
EBA-5                27                    4.3
EBA-6        17            7.4
如乙烯/丙烯酸烷基酯共聚物熔融指数数值为小于1到约10所表明的，本发明中有用的乙烯/丙烯酸烷基酯共聚物其分子量可有很大差异。值得一提的是EBA-5和EBA-6，其MI分别为4.3和7.4g/10min。EMA-3也值得一提，其MI为2g/10min。
在特别优选的实施方案中，当所述基础树脂含乙烯/丙烯酸烷基酯共聚物时，所述乙烯/丙烯酸烷基酯共聚物为在管式反应器中制得的类型。
本发明的组合物可通过将所述组分混合在一起制备。采用干混或熔融共混可有效地制备挤出和层压粘合剂组合物。
本发明的组合物可另外包含小量的粘合剂领域中常用并熟知的任选物质。这类物质包括聚合物材料中使用的常规添加剂(包括增塑剂)、稳定剂(包括粘度稳定剂和水解稳定剂)、主抗氧剂和辅助抗氧剂、紫外线吸收剂、抗静电剂、染料、颜料或其他着色剂、无机填料、阻燃剂、润滑剂、增强剂(如玻璃纤维和薄片)、发泡或起泡剂、加工助剂、滑爽添加剂、抗粘连剂(如硅石或滑石)、脱模剂、增粘性树脂和/或其混合物。这些添加剂见述于Kirk Othmer的Encyclopedia ofChemical Technology(化工技术百科全书)。
这些常规的组分在本发明的组合物中的用量通常为0.01-15％重量，优选0.01-10％重量，只要其不降低所述组合物的基本和新特性且不显著地负面影响所述组合物的粘合性(这类添加剂的重量百分数不包括在本发明的简述部分中所规定的组合物总的重量百分数内)。通常，许多这类添加剂的用量可为0.01-5％重量。
组合物中这类常规组分的任选结合可通过任何已知的工艺进行。这样的结合可例如通过干混、通过挤出各种组分的混合物、通过常规的母料技术等进行。
本发明的粘合剂组合物可干混，然后在双螺杆挤出机中熔融共混并如本领域内众所周知的那样造粒。随后，这些熔融共混的树脂可通过多种方法和工艺被转化和施用。例如，所述粘合剂可通过流延或吹膜模头挤出法被转化为膜，该粘合剂膜可被层压到适当的基材如金属或聚烯烃上。或者，所述粘合剂组合物可作为聚烯烃的一个或两个表面上的皮层与其他聚烯烃共挤出以生产更经济的粘合剂膜。作为又一选择，共挤出的膜可结合极性防渗树脂(如聚酰胺、乙烯/乙烯醇共聚物(EVOH)或聚酯)而制造(用本发明的粘合剂组合物直接粘结到所述极性防渗材料上)。这些粘合剂膜可通过热活化所述粘合剂膜被层压到各种基材上。热活化可通过多种方法进行，包括但不限于直接与加热板或滚筒接触、吸收红外能、直接在烤箱中加热或通过射频频率或微波辐射活化。
在本发明的粘合剂组合物的另一应用中，所述粘合剂可采用本领域内众所周知的工艺(包括例如挤出层压、挤出涂布、共挤出层压和共挤出涂布)直接涂布到基材上。本发明的粘合剂组合物可用来粘结极性防渗树脂如EVOH、聚酰胺或聚酯。一些所述粘合剂组合物也可用来粘结金属如钢、铝、铜和黄铜，以及粘结聚烯烃如聚乙烯、乙烯共聚物和聚丙烯。
如上文所指出的，自高压自由基法制得的乙烯和马来酸酐(或其同类物)的共聚物与适合的非官能化的基于乙烯的聚合物的组合已见公开用作聚酰胺冲击改性剂。高度官能化的乙烯共聚物，如乙烯/马来酸单乙酯(E/MAME)，其本身不是好的冲击改性剂。为赋予作为聚合物改性剂的韧性，伴随使用的基于乙烯的聚合物得为柔软的PE，同时具有较低的结晶度和/或较低的玻璃化转变温度(Tg)。例如，LDPE(较硬的PE)和E/MAME的组合不能提供良好的抗冲击性以增韧聚酰胺。
但在需要高粘合强度的应用中，E/MAME自身可用作粘合剂树脂。此外，例如在挤出或层压聚酰胺(尼龙)/粘结层/PE复合结构的制备中，如本文所述的LDPE和E/MAME的组合可用作优良的粘结层。
本发明的粘合剂组合物能粘结金属和聚烯烃，能在相当低的温度下活化，并易于作为游离或共挤出膜加工而不需要插入中间层或离型纸。此外，已经发现这些粘合剂组合物可能在剥离试验中内聚破坏。内聚破坏是一种理想的性质，因为其可能是粘结强度高粘结强度高于粘合剂的内聚强度的程度的指示。
内聚破坏也提供方便的直观测试以当其他测试方法不便使用时确保多层结构恰当粘结。最后，在粘合剂的内聚破坏模式和产品投用后粘结强度的保持之间看起来有很大的相关性。
因此，本发明提供了对金属基材和许多聚合物材料具有优异的粘结性、产生高剥离强度的粘合剂层的粘合剂组合物。在如建筑物护墙板和管道涂层等物品的生产中，本发明也允许使用相当低的活化温度。
本发明优选的树脂和粘合剂组合物可用在多种应用中，并取决于具体的应用具有不同的性质。某些优选的粘合剂的一种应用是建筑工业中建筑物护墙板的制造，其中所述护墙板呈复合结构的形式，所述复合结构包含被粘结到聚烯烃芯材(如聚乙烯)上的金属基材如铝或钢。如上文所指出的，为粘结聚合物如聚乙烯到金属上，优选基础树脂选自MPE、乙烯与醋酸乙烯酯的共聚物或乙烯与丙烯酸烷基酯的共聚物。本发明的这些优选的粘合剂组合物用来粘结金属基材到聚乙烯芯材上。在这样的应用中，粘合剂层提供聚烯烃到金属基材上的优良粘合是很重要的。此外，粘合剂在应用过程中内聚破坏将是理想的并应相对易于配制和使用。已经发现本发明的粘合剂组合物提供对金属基材和许多聚合物材料的优异的粘合。所述粘合剂组合物可被用作自支承性膜，使其易于加工和处理。
由于当加工成膜并在低温下粘结时其高剥离强度和低表面粘性的独特组合，本发明的优选粘合剂可用于制造铝和钢建筑物护墙板。
预期安装在地下的钢管或管道系统必须带保护层以防腐蚀。这通常通过用粘合剂涂层或底漆涂覆、然后用一层塑料护套材料包住管道的两步程序实现。所述底漆常常由热固性环氧树脂粉末组成，所述环氧树脂粉末在施用了所述粉末的加热管上熔合。所述护套材料常常由高密度聚乙烯组成。
保护性地涂覆一定长度管道的常规方法是旋转并输送加热管水平通过其中安装了一排喷粉枪的小室。当管道行进通过小室时，所述喷粉枪将颗粒物底漆材料喷射到管道圆周周围。小室的下游是螺旋形的缠绕装置，所述缠绕装置以螺纹样式缠绕护套材料，如美国专利3,616,006中的公开。
前述方法有若干缺点。首先，用来旋转和推进管道的输送系统其建造和维护价格昂贵。第二，特别是对于较小直径的管道，底漆难以在管上获得均匀的涂布，且也有大量的过喷从而造成底漆材料的浪费。第三，用螺旋法施用的护套材料在搭接处常有接合弱的问题，且在管上有径向或轴向焊缝覆盖差的问题。当用高密度聚乙烯作为外部护套材料时，螺旋缠绕的缺点更大。已用护套材料螺旋缠绕的管道常表现出相当差的保护性涂层低温粘合性。第四，这种方法仅可用在工厂装置中，而不能用来在安装地点更新管道涂层。
为克服上述缺点，人们探索了保护性涂覆管道的其他方法。例如，目前优选的给管道上护套的方法采用“十字头(cross-head)”挤出技术，也称“直通”或“内型”法。这需要将非旋转的管道水平传输通过环形喷嘴或挤出机头，随着管道穿过挤出机头，挤出机可在管上挤出粘合剂膜的管状涂层和护套材料。但还有必要提供在十字头挤出机上游用底漆材料涂覆一定长度的非旋转管的装置和方法(参见美国专利6,589,346)。
消除用于管道涂覆的螺旋缠绕法或十字头挤出法中底漆的使用将是理想的。本发明的组合物提供对金属的足够粘合，可使多层结构(如管状共挤出膜)粘着到管道上而无需底漆。因此，本发明提供了包含本发明的组合物的管道涂层。
尽管参照其优选实施方案对本发明作了具体展示和描述，但本领域技术人员会理解在不偏离本发明的精神和范围的前提下，可对形式和细节作各种改变。
下面的实施例仅是示例性的，不应理解为限制本文所描述和/或要求的本发明的范围。
实施例
所用材料
M-1为聚乙烯/马来酸酐接枝共聚物，熔融指数(MI)为1.5，密度为0.93g/cc，可从DuPont以Fusabond
Figure G05825251420070130D000151
E MB226D买到。
F-1为聚乙烯/马来酸单乙酯共聚物(E/MAME 90.5/9.5％重量)，MI为30。
F-2为聚乙烯/马来酸酐共聚物(E/MAH 96/4％重量)，MI为80。
LDPE-1为低密度聚乙烯，可从Equistar以商品名NA940买到，MI为0.25，密度为0.918g/cc。
MPE-1为用茂金属催化制备的低密度乙烯/辛烯共聚物，可从DuPont Dow Elastomers以商品名Engage
Figure G05825251420070130D000152
8180买到，MI为0.5，密度为0.863g/cc。
PA-1为尼龙6，可从BASF以商品名Ultramid
Figure G05825251420070130D000153
B35买到。
EBA-5为乙烯/丙烯酸正丁酯共聚物(27％重量的丙烯酸正丁酯)，MI为4.3。
EMA-3为乙烯/丙烯酸甲酯共聚物(9％重量的MA)，MI为2。
EVA-1为乙烯/醋酸乙烯酯共聚物(21％重量的VA)，MI为1.5。
PP-1为聚丙烯，可从Dow Chemical以商品名DX5E98买到，MI为3.4，密度为0.90g/cc。
HIP-1为高抗冲苯乙烯，可从Nova Chemicals以商品名PX510买到，MI为3.4，密度为0.90g/cc。
除非另有指出，否则所给份数和百分数均为按重量计。
熔融指数(MI)为在规定的温度和压力条件下聚合物通过指定毛细管的质量流率。本文中报道的熔融指数是按ASTM 1238于190℃下用2160g符合测定的，所报道的MI值的单位为克/10分钟。
表1中的实施例1-3给出了用本发明的组合物作为3-层尼龙/粘结层/LDPE吹塑膜的粘结层所获得的粘合。PA-1/粘结层/LDPE-1的三层共挤吹塑膜(厚度约为1.0密耳/0.5密耳/1.5密耳)在吹膜生产线上用直径为5厘米(2-英寸)的Brampton模头制备。粘结层为LDPE-1和F-1的干混混合物，F-1的含量分别为5、10和20％重量。从该3-层膜上切下一英寸宽的条。于第二天用手剥离试验测试条的粘合特性。
所有三种3-层膜均展现出优良的层间粘合，该粘合使层间不可分开。即便F-1的含量为5％重量，组合物也提供优良的粘合。这表明本发明的粘合剂组合物可从E/MAME的组合和廉价的LDPE(或其他PE)制备而无需熔融共混，这样的组合物能提供高粘合强度。
表1 LDPE-1/粘结层/PA-1的三层吹塑膜
粘结层组合物
实施例          (干混重量比)           粘合
1               LDPE-1/F-1(95/5％)     不可分开
2               LDPE-1/F-1(90/10％)    不可分开
3               LDPE-1/F-1(80/20％)    不可分开
实施例4-8
用小型实验室规模的吹塑膜生产线制备表2中所列组合物的吹塑膜样品(约为2-4密耳厚)。然后将该膜用作粘合剂层来制备铝箔/粘合剂/铝箔的三层复合结构。铝箔为1密耳厚。该三层复合结构按如下程序制备：
将层压机设定到指定的温度。按铝箔/粘合剂(吹塑膜)/铝箔的顺序堆叠来组装复合结构。堆叠好的层在层压机中预热5分钟，然后在44psi的压力下压30秒钟以形成层压复合结构。让该结构冷却到室温。从该3-层膜上切下一英寸宽的条。于第二天用手剥离试验测试条的粘合特性。
数据汇总在表2中。剥离试验的报告如下：
a)N表示无粘合，即复合结构很容易剥离开。
b)P表示有粘合，但铝箔和粘合剂层可分开而不撕坏铝箔。
c)Y表示粘合强度太强，以致无法不撕坏铝箔而剥离开。
表2铝/粘合剂/铝层压物剥离试验
Figure G05825251420070130D000171
如表2中所示，在指定的压塑条件下，E/MAME与PP或LDPE的共混物(实施例4-8)对铝箔没有足够的粘着力。铝箔和共混粘合剂很容易剥离开。
纯粹的E/MAME(对照实施例C1)作为粘结层能粘合铝箔。但通过手剥离，明显可见铝箔和E/MAME层间的粘着力不是很强。复合结构无需撕坏铝箔即剥离开。
实施例9-44
表3中所列组合物的层压物样品按实施例4-8的程序制备。
剥离强度用90-度剥离强度试验进行评估，试验按ASTM 904进行，试验速度为50毫米/分钟。结果汇总在表3中。
表3铝/粘合剂/铝层压物剥离试验
层压条件       剥离强度
实施例    粘合剂组合物                   (温度/时间)    (克/英寸)
C2        F-1                            110℃/20sec    766
C3        F-1                            110℃/23sec    684
C4        F-1                            120℃/20sec    1021
C5        F-1                            130℃/20sec    1007
C6        F-1                            140℃/20sec    1136
9         EBA-5/F-1(70/30％)             100℃/20sec    532
10        EBA-5/F-1(70/30％)             110℃/3sec     1454.5
11        EBA-5/F-1(70/30％)             110℃/20sec    1754
12        EBA-5/F-1(70/30％)             120℃/20sec    2164
13        EBA-5/F-1(70/30％)             130℃/20sec    1223
14        EBA-5/F-1(70/30％)             140℃/20sec    1596
15        EVA-1/F-1(80/20％)             100℃/20sec    2005
16        EVA-1/F-1(80/20％)             110℃/3sec     1943
17        EVA-1/F-1(80/20％)             110℃/20sec    2000
18        EVA-1/F-1(80/20％)             120℃/20sec    2512
19        EVA-1/F-1(80/20％)             130℃/20sec    2630
20        EVA-1/F-1(80/20％)             140℃/20sec    2724
21        EMA-3/F-1(70/30％)             100℃/20sec    387
22        EMA-3/F-1(70/30％)             110℃/3sec     1706
23        EMA-3/F-1(70/30％)             110℃/20sec    1787
24        EMA-3/F-1(70/30％)             120℃/20sec    1938
25        EMA-3/F-1(70/30％)             130℃/20sec    2681
26        EMA-3/F-1(70/30％)             140℃/20sec    2325
27        MPE-1/F-1(70/30％)             100℃/20sec    1297
28        MPE-1/F-1(70/30％)             110℃/3sec     2023
29        MPE-1/F-1(70/30％)             110℃/20sec    1867
30        MPE-1/F-1(70/30％)             120℃/20sec    2114
31        MPE-1/F-1(70/30％)             130℃/20sec    2414
32        MPE-1/F-1(70/30％)             140℃/20sec    2294
33        EVA-1/F-2(70/30％)             100℃/20sec    1721
34        EVA-1/F-2(70/30％)             110℃/3sec     2093
35        EVA-1/F-2(70/30％)             110℃/20sec    1713
36        EVA-1/F-2(70/30％)             120℃/20sec    2393
37        EVA-1/F-2(70/30％)             130℃/20sec    2058
38        EVA-1/F-2(70/30％)             140℃/20sec    3593
39        EVA-1/F-2/HIP-1(56/24/20％)    100℃/20sec    1484
40        EVA-1/F-2/HIP-1(56/24/20％)    110℃/3sec     2916
41        EVA-1/F-2/HIP-1(56/24/20％)    110℃/20sec    2645
42        EVA-1/F-2/HIP-1(56/24/20％)    120℃/20sec    3042
43        EVA-1/F-2/HIP-1(56/24/20％)    130℃/20sec    2971
44        EVA-1/F-2/HIP-1(56/24/20％)    140℃/20sec    3006
纯粹的E/MAME(对照实施例C2-C6)作为粘结层能粘着铝箔。但粘合强度不是对所有应用都足够强。
实施例4-44表明E/MAME或E/MAH与柔软的乙烯共聚物(如乙烯/醋酸乙烯酯和乙烯/丙烯酸烷基酯以及MPE)的组合能提供意想不到的优良的金属粘着力。
E/MAME与EVA-1、EBA-5或EMA-3的共混物均展现出对铝箔的优异粘着力。不撕坏铝箔则无法将复合结构剥离。因此，该粘合破坏为内聚破坏。此外，E/MAME与EVA的共混物的粘合引发温度较纯粹的E/MAME要低得多。
上文在一定的具体程度上对本发明进行了描述和举例，但应理解下面的权利要求不受限于此，而是与各项权利要求的内容和其等价物限定的范围相当。

Claims (12)

1.一种聚合物粘合剂组合物，所述组合物包含：
(a)烯烃与3％重量-15％重量的官能化共聚单体的共聚物，其通过高压自由基聚合法得到，所述官能化共聚单体选自马来酸酐、马来酸单酯、马来酸二酯、富马酸单酯及其混合物；和
(b)聚合物基础树脂，所述聚合物基础树脂选自线形低密度聚乙烯、茂金属聚乙烯、乙烯/丙烯共聚物、乙烯/丙烯/二烯三元共聚物、聚丙烯均聚物及共聚物、乙烯/醋酸乙烯酯共聚物、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、衍生自乙烯/丙烯酸和/或甲基丙烯酸共聚物的盐、聚氯乙烯、氯化聚氯乙烯和聚苯乙烯及其混合物；
其中所述粘合剂组合物包含5-50％重量的组分(a)和50-95％重量的组分(b)。
2.权利要求1的组合物，其中所述官能化共聚单体为选自马来酸单酯、富马酸单酯及其混合物的单体。
3.权利要求1的组合物，其中所述官能化共聚单体为选自马来酸酐的单体。
4.一种粘合剂膜，所述粘合剂膜包含：
(a)烯烃与3％重量-15％重量的官能化共聚单体的共聚物，其通过高压自由基聚合法得到，所述官能化共聚单体选自马来酸酐、马来酸单酯、马来酸二酯、富马酸单酯及其混合物；和
(b)聚合物基础树脂，所述聚合物基础树脂选自线形低密度聚乙烯、茂金属聚乙烯、乙烯/丙烯共聚物、乙烯/丙烯/二烯三元共聚物、聚丙烯均聚物及共聚物、乙烯/醋酸乙烯酯共聚物、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、衍生自乙烯/丙烯酸和/或甲基丙烯酸共聚物的盐、聚氯乙烯、氯化聚氯乙烯和聚苯乙烯及其混合物； 
其中所述粘合剂膜包含5-50％重量的组分(a)和50-95％重量的组分(b)。
5.一种多层复合结构，所述多层复合结构具有包含粘合剂组合物的粘合剂层，其中所述粘合剂组合物包含：
(a)烯烃与3％重量-15％重量的官能化共聚单体的共聚物，其通过高压自由基聚合法得到，所述官能化共聚单体选自马来酸酐、马来酸单酯、马来酸二酯、富马酸单酯及其混合物；和
(b)聚合物基础树脂，所述聚合物基础树脂选自线形低密度聚乙烯、茂金属聚乙烯、乙烯/丙烯共聚物、乙烯/丙烯/二烯三元共聚物、聚丙烯均聚物及共聚物、乙烯/醋酸乙烯酯共聚物、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、衍生自乙烯/丙烯酸和/或甲基丙烯酸共聚物的盐、聚氯乙烯、氯化聚氯乙烯和聚苯乙烯及其混合物；
其中所述粘合剂组合物包含5-50％重量的组分(a)和50-95％重量的组分(b)。
6.权利要求5的多层复合结构，其中所述复合结构为多层膜或片。
7.权利要求6的多层复合结构，其中所述结构包含至少两个粘合剂层。
8.权利要求7的多层复合结构，其中所述结构包含至少三个粘合剂层。
9.一种管道涂层，所述管道涂层包含粘合剂组合物，其中所述粘合剂组合物包含：
(a)烯烃与3％重量-15％重量的官能化共聚单体的共聚物，其通过高压自由基聚合法得到，所述官能化共聚单体选自马来酸酐、马来酸单酯、马来酸二酯、富马酸单酯及其混合物；和
(b)聚合物基础树脂，所述聚合物基础树脂选自线形低密度聚乙烯、茂金属聚乙烯、乙烯/丙烯共聚物、乙烯/丙烯/二烯三元共聚物、 聚丙烯均聚物及共聚物、乙烯/醋酸乙烯酯共聚物、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、衍生自乙烯/丙烯酸和/或甲基丙烯酸共聚物的盐、聚氯乙烯、氯化聚氯乙烯和聚苯乙烯及其混合物；
其中所述粘合剂组合物包含5-50％重量的组分(a)和50-95％重量的组分(b)。
10.一种物品，所述物品包含粘合剂组合物，所述粘合剂组合物包含：
(a)烯烃与3％重量-15％重量的官能化共聚单体的共聚物，其通过高压自由基聚合法得到，所述官能化共聚单体选自马来酸酐、马来酸单酯、马来酸二酯、富马酸单酯及其混合物；和
(b)聚合物基础树脂，所述聚合物基础树脂选自线形低密度聚乙烯、茂金属聚乙烯、乙烯/丙烯共聚物、乙烯/丙烯/二烯三元共聚物、聚丙烯均聚物及共聚物、乙烯/醋酸乙烯酯共聚物、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、衍生自乙烯/丙烯酸和/或甲基丙烯酸共聚物的盐、聚氯乙烯、氯化聚氯乙烯和聚苯乙烯及其混合物；
其中所述粘合剂组合物包含5-50％重量的组分(a)和50-95％重量的组分(b)。
11.权利要求10的物品，其中所述物品为粒料或建筑物护墙板。
12.权利要求11的物品，其中所述官能化共聚单体选自马来酸酐、马来酸单酯、马来酸二酯及其混合物。 
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CN101027374A (zh) 2007-08-29
JP2008508403A (ja) 2008-03-21
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KR101201592B1 (ko) 2012-11-14
US7767311B2 (en) 2010-08-03
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