CN1190976A - 改性异单烯烃/对烷基苯乙烯共聚物的接枝固化 - Google Patents
改性异单烯烃/对烷基苯乙烯共聚物的接枝固化 Download PDFInfo
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- CN1190976A CN1190976A CN96195545A CN96195545A CN1190976A CN 1190976 A CN1190976 A CN 1190976A CN 96195545 A CN96195545 A CN 96195545A CN 96195545 A CN96195545 A CN 96195545A CN 1190976 A CN1190976 A CN 1190976A
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Abstract
从一种混合物制备的可固化的和已接枝固化的聚合物的组合物,该混合物包括a)弹性体聚合物,它含有约0.01-约10mol%的沿弹性体聚合物链和侧挂于聚合物链的无规分布的Y酯基,该Y酯基具有结构式(Ⅰ),其中R2和R3独立地选自氢和含有1-约6个碳原子的烷基和R4选自氢,含有1-约28个碳原子的烷基,芳基和含有2-约28个碳原子的链烯基;和b)至少一种可自由基聚合的单体。本发明还提供了制备接枝固化聚合物组合物的方法,包括形成具有以上组分(a)和(b)的混合物和让该混合物经受自由基聚合条件。侧挂于弹性聚合物链的该Y酯基,例如在异丁烯/对—甲基苯乙烯共聚物链中存在的(甲基)丙烯酸苄基酯基团,能够参加与单官能度或多官能度可自由基聚合的单体的自由基引发的反应,以生产具有各种物理性能的不寻常平衡的接枝交联组合物。这些组合物可以成型为成型制品如薄膜,涂层和粘合剂层和模塑制品,并经受自由基聚合条件生产出交联的成型制品。
Description
本申请是共同未决的US系列号08/402,792(1995年3月13日提交)的部分续申请;后者是1994年1月14日提交的US系列号08/181,713、现为US专利5,430,118的分案申请;而后者是现已放弃的1992年5月11日提交的US系列号07/880,922的分案申请;后者又是1989年11月27日提交的US系列号07/442,028、现为US专利5,162,445的分案申请。
本发明涉及含有不饱和的酯改性弹性聚合物的接枝固化组合物以及通过该聚合物与反应活性单体相互作用制备组合物的方法。
在现有技术中已知的是具有共轭二烯烃不饱和度的某些弹性聚合物能够通过让该聚合物与一种或多种可自由基聚合的单体在自由基引发剂存在下进行反应加以接枝固化。例如US专利3,968,185教导了弹性体如异丁烯和异戊二烯的脱氢卤化共聚物(丁基橡胶)或乙烯/丙烯和5,6-二亚烷基-2-降冰片烯的弹性三元共聚物能够通过弹性体与可自由基聚合的单体如苯乙烯在自由基引发剂存在下进行反应来交联。在此类弹性体中存在的游离内二烯烃不饱和基团有利于单体链加成到聚合物骨架上和有利于复杂的聚合物网络的形成,其中一些是连接不同弹性体分子的接枝网络。这些可交联的组合物经配制后能够提供具有不寻常的物理性能平衡的固化产物,并可以用作涂料、粘合剂和用于模塑和挤塑加工的机械、汽车和工业制品。
对于卤化丁基橡胶的类似物最近已发现它包括C4-C7异单烯烃例如异丁烯和对-烷基苯乙烯如对-甲基苯乙烯的无规共聚物的卤化产物,如US专利5,162,445中所公开的那样。虽然这些物质没有烯属骨架不饱和度,但苄基卤素例如溴的存在使得可以使用氧化锌/硬脂酸固化体系更容易地将该聚合物交联或固化。还有,这些共聚物的官能化变体可以通过聚合物分子中存在的苄基卤素被可与其反应的试剂进行亲核取代,提供含有胺、酸、酯、酰胺和类似官能团的聚合物而制得。接枝的聚合物也可以通过接枝反应来制得,在该反应中卤化共聚物在溶液中与聚合亲核试剂如聚苯乙烯基锂反应。这些接枝反应导致生产出溶剂可溶的接枝共聚物,但无法获得与上述品种类似的交联接枝共聚物。
本发明提供可固化的聚合物组合物,它包括由以下组分组成的混合物:
a)弹性体聚合物,它含有约0.01-约10mol%的沿弹性体聚合物链和侧挂于弹性体聚合物链无规分布的Y酯基,该Y酯基由以下结构表示:其中R2和R3独立地选自氢和含有1-约6个碳原子的烷基和R4选自氢,含有1-约28个碳原子的烷基,芳基和含有2-约28个碳原子的链烯基;和
b)至少一种可自由基聚合的单体。
本发明还提供制备接枝固化聚合物组合物的方法,包括:形成以上列举的(a)和(b)的混合物和让该混合物经受自由基聚合条件。
本发明还通过让包括以上列出的组分(a)和(b)的混合物经受自由基聚合条件而提供如此制备的固化反应产物。
侧挂于弹性体聚合物链的Y酯基,例如在异丁烯/对-甲基苯乙烯共聚物链上存在的(甲基)丙烯酸苄基酯基,能够参加与单官能度或多官能度可自由基聚合的单体的自由基引发的反应,得到具有不寻常的物理性能平衡的接枝交联组合物。这些组合物经受自由基聚合条件,生产出交联的(硫化的)成型制品,如薄膜,涂层,粘合剂和热熔层,以及挤塑或模塑制品。
在本发明中作为组分(a)存在的弹性体聚合物包括含有侧挂官能团的任何聚合物或共聚物,该官能团可与相应的酸或盐反应形成侧挂于聚合物链上的Y酯基。此类官能团包括羟基和胺官能团(例如在聚丁二烯、聚异戊二烯或EPDM弹性体的含羟基或胺的聚合物中所存在的羟基和胺官能团),或卤素官能团(例如在异丁烯与异戊二烯或对-烷基苯乙烯的共聚物中存在的卤素官能团)。
本发明特别适用,其中组分(a)包括C4-C7异单烯烃和对-烷基苯乙烯的苄基酯官能化共聚物,该共聚物是通过C4-C7异单烯的卤化共聚物(下面将要描述)与具有下式的亲核试剂,在使得卤化共聚物结构中存在的至少部分和优选基本上所有的苄基卤原子经亲核取代反应被相应的酯基置换的一种反应条件下,进行反应而制得的:其中M是氢,金属离子或鎓离子以及R2,R3和R4如上所述。在上式中,R2优选是氢或甲基,R3优选是氢和R4优选是氢或C3-C12链烯基。
卤化的C4-C7异烯烃/对-烷基苯乙烯起始原料是C4-C7异烯烃(如异丁烯)和对-烷基苯乙烯共聚单体(优选含有至少约80wt%、更优选至少约90wt%的对位异构体的对-甲基苯乙烯)的无规共聚物的卤化产物,其中在苯乙烯单体单元上存在的至少一些烷基取代基含有卤素。优选的起始原料体现特征为含有沿着聚合物链无规间隔的以下单体单元的异丁烯共聚物:
其中R和R′独立地是氢,低级烷基,优选C1-C4烷基,和X是溴或氯,和其中共聚物另外基本上没有处在环上的卤素或没有在聚合物骨架链上的卤素。优选地,R和R′各自是氢。在共聚物结构中存在的至多约60mol%的对-烷基苯乙烯可以是以上卤化结构(2)。
最有用的此类物质是含有约0.5-约20mol%对-甲基苯乙烯的异丁烯和对-甲基苯乙烯的弹性无规共聚物,其中至多约60mol%的在苄基环上存在的甲基取代基含有溴或氯原子,优选溴原子。这些共聚物具有基本上均匀的组成分布,以使至少95wt%的聚合物所具有的对-烷基苯乙烯含量是在聚合物的平均对-烷基苯乙烯含量的10%范围内。其特征还在于低于约7,更优选低于约5.0的窄分子量分布(Mw/Mn),优选的粘均分子量在约300,000-约2,000,000范围内和优选的数均分子量在约10,000,优选25,000-约1,000,000范围内,由凝胶渗透色谱法测定。
通过使用路易斯酸催化剂让单体混合物进行淤浆聚合,然后在卤素和自由基引发剂如热和/或光和/或化学引发剂存在下在溶液中进行卤化,优选进行溴化,来制备共聚物。
优选的溴化共聚物一般含有约0.01-约10mol%的溴甲基,其中大部分是一溴甲基,在共聚物中存在少于0.05mol%的二溴甲基取代基。这些共聚物,它们的制备方法,它们的固化和接枝方法或从这些方法得到的官能化聚合物更特别地公开于US专利5,162,445中,该专利的整个内容被引入本文供参考。这些共聚物的丙烯酸和甲基丙烯酸酯官能化衍生物特别地公开于该专利的实施例112 F-1和112 F-2中。
上述亲核取代反应优选通过使用一种溶剂体系在溶液中进行,该溶剂体系会溶解卤化异烯烃/对-烷基苯乙烯共聚物和得到聚合物和亲核试剂的溶液或分散液以在基础聚合物的苄基卤和亲核试剂之间实现紧密接触。合适的溶剂包括苯,甲苯,链烷烃如庚烷、己烷和环己烷以及含氧的溶剂或溶剂混合物如四氢呋喃或它与低级醇的混合物。
该反应优选在温和反应条件下进行,以避免交联或凝胶化产物的形成并最大程度减少不需要的副反应。优选的反应温度是约20-100℃。通过使用亲核试剂的鎓盐(即四丁基铵盐)作为反应剂,在温和反应条件下有利于所需反应产物的形成。
用来形成亲核试剂的酸是含有与羰基共轭的烯属不饱和键的那些,例如丙烯酸,甲基丙烯酸,山梨酸,肉桂酸和类似物,以及它们的混合物。所得到的反应产物的特征为一种包括至少约80wt%含有4-7个碳原子的聚合异烯烃和约0.05-约20wt%包含以下无规分布结构的混合结构的芳族单体单元的无规共聚物:其中R和R′独立地选自氢和C1-C4烷基和Y如以上所定义。当聚合物中存在的所有卤素被完全置换,所得到的产物是三元共聚物,当卤素仅被部分置换时,所得到的产物是还包括一些如以上单体单元2所定义的未反应的含卤素的单体单元的三元共聚物。更优选的物质是含有至少约95mol%的聚合异丁烯和余量的由较多对-甲基苯乙烯和较少4-(丙烯酰氧基-甲基)苯乙烯、4-(甲基丙烯酰氧基-甲基)苯乙烯、4-(肉桂酰氧基-甲基)苯乙烯或4-(2,4-己二烯酰氧基-甲基),苯乙烯组成的混合物的一种三元共聚物。
亲核置换反应优选在一定条件和一定时间内进行,以使得至少约25wt%、更优选至少约50wt%和最优选基本上所有的苄基卤均被Y酯基亲核试剂所置换。所得到的官能化聚合物一般含有约0.01-约10mol%的Y酯基,更优选约0.05-约2.0mol%的Y酯基,并且也可以含有一些残基、未反应的苄基卤。
在本发明中用作组分(a)的酯官能化弹性体也包括乙烯/丙烯和至多约10wt%的非共轭二烯烃(EPDM)如二环戊二烯、1,4-己二烯、5-亚甲基-2-降冰片烯和5-亚乙基-2-降冰片烯的酯改性的弹性三元共聚物。这些弹性体的酯官能化衍生物可通过在齐格勒-纳塔聚合条件下让乙烯、丙烯和醇(例如5-降冰片烯-2-甲醇)、非共轭二烯烃的衍生物进行聚合反应,得到EPDM的醇官能化衍生物而制得,如US专利5,153,282(尤其是实施例18)中所公开的,该专利的整个内容被引入本文供参考。该产物与合适的酰氯的常规反应得到了含有连接于和侧挂于聚合物链的二烯烃部分的、如上所定义的Y酯基的改性EPDM聚合物。
酯官能化弹性聚合物的接枝固化是通过在自由基引发剂存在下与可自由基聚合的一种单体或多种单体混合物的反应来进行的,进行的时间足以将基本上所有的单体原料转化成接枝和交联聚合物链。选择单体以得到具有可变分子量的大交联体。作为简单的接枝固化,其中由单官能度(单不饱和)单体的聚合物链组成的大交联体通过使用合适的聚合物可溶或聚合物不可溶的单体产生。除单官能度单体外,在可聚合的组合物中还包含少量的一种或多种多官能度(多不饱和)单体,从而形成了互穿网络,后者然后产生与接枝固化的网络相互交织的独立网络。
有用的单官能度单体包括单烯属不饱和单体,如苯乙烯和取代的苯乙烯,丙烯酸和甲基丙烯酸烷基酯,丙烯酸,甲基丙烯酸,丙烯腈,甲基丙烯腈,乙烯基酯,乙烯基醚,丙烯酰胺,甲基丙烯酰胺,乙烯基咔唑,氯乙烯,乙酸乙烯酯,乙烯基吡啶,乙烯基吡咯烷酮,马来酸或酸酐以及它们的混合物。
除单官能度单体外另外还可以被使用的合适多官能度单体包括二烯烃类,如丁二烯或异戊二烯,二或三乙烯基苯,二或三丙烯酸或甲基丙烯酸亚烷基二醇酯及其混合物。优选的多官能度单体包括二乙烯基苯,二甲基丙烯酸乙二醇酯和二甲基丙烯酸1,6-己二醇酯。
单体,它们的浓度和最佳反应条件的选择使得有可能控制组合物交联密度,复合极性,化学和环境性能,机械性能,外观(透明-不透明),导电性和其它有用的和独特的性能。
可固化的组合物是通过首先形成酯官能化弹性聚合物和一种或多种单体原料以及视具体情况而存在的弹性体的添加溶剂的混合物来制备。这里使用的术语混合物指:通过将聚合物可溶单体和聚合物混合形成溶胀的或液体的物质所形成的溶液,或通过将聚合物直接与聚合物不溶性单体或与已吸附该聚合物不溶性单体的载体如硅石或炭黑进行机械混合所形成的分散液。
可固化的组合物含有约1-约100重量份的单体原料/每100重量份的酯官能化弹性体,更优选约10-约60重量份的单体原料。该单体组合物含有0-约25wt%一种或多种多官能度单体。
用来引发交联的自由基源包括辐射,有机过氧化物,有机氢过氧化物,偶氮化合物,和无机氧化-还原自由基体系。
辐射源包括诸如γ和β辐射的辐射,紫外线和可见光辐射,电子束辐射或其它任何高能量辐射。辐射交联可通过形成酯改性聚合物和交联单体的混合物,将混合物成型和让成型的制品接受足以使组合物交联的合适剂量的辐射来进行。
可使用的化学引发剂包括二烷基和二酰基过氧化物。
二烷基过氧化物具有通式R-O-O-R′,其中R和R′能够是相同的或不同的伯、仲或叔烷基,环烷基,芳烷基,或杂环基。其中合适的过氧化物是过氧化二枯基,过氧化二叔丁基,过氧化叔丁基枯基和2,5-二甲基-2,5-双(叔丁基过氧基)己烷。
过氧化二酰基具有通式RC(O)OOC(O)R′,其中R和R′是相同的或不同的烷基,环烷基,芳烷基,芳基或杂环基团。合适的一些过氧化二酰基的例子是过氧化二月桂酰基,过氧化二苯甲酰基,过氧化十六烷酰基,过氧化二癸酰基,过氧化二(2,4-二氯苯甲酰),过氧化二异壬酰基和过氧化2-甲基戊酰基。
本领域专业人员很清楚,用于交联聚合物或引发聚合反应的任何有机过氧化物都包括在本发明中。
对用于本发明中的过氧化物进行选择的基础包括过氧化物在混合和/或固化温度下的半衰期和所选择过氧化物在体系中的相容性。
适用于本发明中的氢过氧化物的例子包括叔丁基过氧氢,枯基过氧氢,2,5-二甲基-2,5-二氢过氧己烷,p-甲烷过氧化氢和二异丙基苯过氧化氢。
在本发明中适合用作自由基引发剂的一些偶氮化合物的例子包括重氮氨基苯,N,N′-二氯偶氮二酰胺,偶氮二羧酸二乙酯和偶氮双(异丁腈)。
当可交联的组合物含有化学引发剂时,它一般以约0.1-约20重量份、更优选约0.5-约5重量份/100重量份可交联组合物的量混入组合物中。交联可如下进行:形成酯改性聚合物、交联单体和化学引发剂的混合物,将该混合物成型,然后在约50℃-约250℃范围内的温度下将成型制品加热约1-约120分钟。
该组合物还可以含有一种或多种加速有机过氧化物分解的叔胺。优选的胺类是在固化温度下可溶于可固化混合物的那些。此类叔胺的例子是三乙胺,三丁胺,和2,4,6-三(二甲氨基)苯酚。
金属羧酸盐也可以用于本发明中以加速过氧化物分解成自由基片段。适用于本发明中的金属羧酸盐的例子是选自铝、钴、钒、铜、钙、铅、汞、锌、锰、镁、锆和铁的金属的环烷酸盐,辛酸盐和树脂酸盐。
本发明的组合物还可以含有合适的吸附剂和填料(增强和非增强型)如硅石,炭黑,碳酸钙,粘土和其它无机填料,以及合成和天然纤维。此类添加剂经选择后应要求它们不干扰或阻断接技聚合反应。
本发明的可固化聚合物组合物可以用于许多应用场合,如薄膜、涂层和粘合剂,以及用于制造模塑制品。固化的薄膜显示出优异的透明性,这使它们在光学应用如汽车挡风玻璃结构中特别有用。含有(甲基)丙烯酸或酸酯和/或丙烯腈接枝单体的组合物可用于制备要求提高耐油性的制品如衬垫和密封片,电线和电缆绝缘体以及类似的应用场合。
下面实施例用来说明本发明。
实施例A
按以下方法制备异丁烯/对-甲基苯乙烯/对-溴甲基苯乙烯基础三元共聚物的甲基丙烯酸酯(MAE)衍生物:
装有顶部搅拌器、连接管和隔膜的5000mL带玻璃夹套的反应器用氮气吹扫。在氮气气氛和室温下,在反应器中装入甲苯(3100mL)和475g包括2.4mol%总对-甲基苯乙烯、包含1.05mol%对-溴甲基苯乙烯并具有门尼粘度65(1+8分钟,125℃)的基础异丁烯/对-甲基苯乙烯/对-溴甲基苯乙烯三元共聚物。通过在室温下搅拌过夜来溶解基础三元共聚物。通过在第二个烧瓶中加入123.6mL氢氧化四丁基铵(在甲醇中,1.0M),110mmol甲基丙烯酸,5.15mmol 4-羟基-二苯甲酮和100mL异丙醇(IPA),并在室温下摇晃烧瓶内的内容物得到无色透明溶液,而在该烧瓶中制备了甲基丙烯酸四丁基铵盐。然后在83℃的循环浴温下将该溶液加入到含有已溶解的基础三元共聚物的烧瓶中。45分钟后,将浴温升高至95℃,并保持7.5小时。然后将浴温降低至70℃,2.5小时后反应经放置冷却。用10mL HCl在1000mL蒸馏水中的溶液骤冷和洗涤黄色粘稠溶液,然后用H2O/IPA(70∶30)洗涤5-6次。通过沉淀将聚合物分离到异丙醇中,然后在1mmHg和80℃下真空干燥48小时。回收的物质的溶液粘度等于起始原料的粘度,官能化聚合物的1H NMR(400MHz,CDCl3)分析表明苄基溴的定量转化。NMR分析结果揭示在聚合物中有0.35mol%的甲基丙烯酸和0.05mol%的二苯甲酮官能团。
实施例B
按照实施例A中所述制备基础三元共聚物的第二种MAE衍生物,只是在反应介质中包含的甲基丙烯酸的量应使得生产出含有0.60mol%甲基丙烯酸酯的官能化聚合物。
实施例1和2
在实施例A和B中制备的酯改性异丁烯/对-甲基苯乙烯聚合物用于制备本发明的接枝交联组合物。
在宽口4盎司瓶中向10g聚合物A和10g聚合物B中添加5g99%苯乙烯。该瓶子用氮气温和吹扫并加以密封。苯乙烯被弹性体吸收形成非常粘稠的溶液。将苯乙烯/聚合物溶液转移至水冷却的微型捏合机(Baker-Perkins)中,混合60秒,然后添加0.07g过氧化月桂酰(Aldrich-97%),并混合60秒。混合物被转移至带有3″×3″×0.06″模腔的三件式模具中,然后在涂有特氟隆的铝片之间固化。固化条件是在105℃和1280psi下历时40分钟。模具被抽空两次以除去其中包含的空气。在完全固化后,从模腔中切下样品。
该交联组合物的组成和特性示于表1中。
表1中数据说明,鉴于用两种溶剂(环己烷(C6H12)和甲乙酮(MEK))的萃取百分率都很低的事实,聚苯乙烯链紧密地结合于交联网络中。环己烷是异丁烯/对-甲基苯乙烯弹性体的溶剂,但不是聚苯乙烯的溶剂;MEK是聚苯乙烯的溶剂但非弹性体的溶剂。苯乙烯片段的不溶性是接枝和不可逆地交联到聚合物骨架上的证据。
表1
●ASTM D-412
实施例 | 1 | 2 |
聚合物ID | A | B |
MAE,mol% | 0.35 | 0.6 |
ML(1+8)125℃,门尼粘度 | 51 | 47 |
颜色(初始) | 中等黄色 | 黑棕色 |
固化条件和性能 | (固化40分钟@105℃) | (固化40分钟@105℃)(96小时后测试@RT) |
外观 | 透明无色 | 透明,褐黄色 |
苯乙烯气味 | 痕量 | 痕量 |
拉伸性能(20′/分钟)● | ||
试样编号 | 4 | 3 |
100%Mod.,MPa | 4.822 | 2.545 |
200%Mod.,MPa | 9.207 | 5.821 |
300%Mod.,MPa | - | 10.370 |
拉伸强度,MPa | 10.370 | 11.25 |
伸长率% | 218 | 317 |
断裂能,焦耳 | 2.025 | 2.387 |
体积溶胀和萃取物1: | ||||
溶剂 | C6H12 | MEK | C6H12 | MEK |
%溶胀 | 261 | 37.8 | 315 | 42 |
萃取物,% | 0.50 | 0.47 | (-1.1) | 0.98 |
1在以上指定的溶剂中在R.T.下萃取72小时后,在称重之后在另一种溶剂中萃取同样的样品,然后加以干燥以测定初始%溶胀和萃取物。
溶剂 | C6H12 | MEK | C6H12 | MEK |
%溶胀 | 269 | 39.6 | 349 | 42.8 |
萃取物,% | 1.25 | 1.19 | 1.36 | 3.34 |
Claims (33)
1、可固化的组合物,其中包括:
a)弹性体聚合物,它含有约0.01-约10mol%沿弹性体聚合物链和侧挂于聚合物链的无规分布的Y酯基,该Y酯基具有以下结构:其中R2和R3独立地选自氢和含有1-约6个碳原子的烷基和R4选自氢,含有1-约28个碳原子的烷基,芳基和含有2-约28个碳原子的链烯基;和
b)至少一种可自由基聚合的单体。
2、权利要求1的组合物,其中所述混合物还含有自由基聚合物引发剂。
3、权利要求1的组合物,其中弹性聚合物是包括至少约80wt%的含有4-7个碳原子的聚合异烯烃和约0.05-约20wt%的包含以下无规分布结构的混合结构的芳族单体单元的无规共聚物:其中R和R′独立地选自氢和C1-C4烷基。
4、权利要求3的组合物,其中C4-C7异烯烃是异丁烯,该共聚物含有至少约90wt%的异丁烯,其中R和R′各自是氢。
5、权利要求4的组合物,其中R2是甲基及R3和R4各自是氢。
6、权利要求4的组合物,其中R2、R3和R4各自是氢。
7、权利要求4的组合物,其中R2和R3各自是氢,R4是C4链烯基。
8、权利要求1的组合物,其中含有约0.05-约2.0mol%所述Y酯基。
9、权利要求3的组合物,其中该混合芳族单体单元的约5-约60mol%含有结构(b)。
10、权利要求3的组合物,其中该弹性共聚物具有数均分子量为约25,000-约1,000,000,组成分布(Mw/Mn)低于约7。
11、权利要求1的组合物,其中可自由基聚合的单体在混合物中以约1-100重量份/100重量份弹性共聚物的量存在。
12、权利要求11的组合物,其中该单体包括从苯乙烯和取代的苯乙烯,丙烯酸和甲基丙烯酸烷基酯,丙烯酸,甲基丙烯酸,丙烯腈,甲基丙烯腈,乙烯基酯,乙烯基醚,丙烯酰胺,甲基丙烯酰胺,乙烯基咔唑,氯乙烯,乙酸乙烯酯,乙烯基吡啶,乙烯基吡咯烷酮,马来酸或酸酐以及它们的混合物中选择的单官能度单体。
13、权利要求12的组合物,其中该单体进一步包括从丁二烯,异戊二烯,二或三乙烯基苯,二或三丙烯酸或甲基丙烯酸亚烷基二醇酯及其混合物中选择的多官能度单体。
14、权利要求12的组合物,其中混合物进一步含有选自有机过氧化物和氢过氧化物的自由基引发剂。
17、权利要求16的方法,其中混合物还含有自由基聚合物引发剂。
18、权利要求17的方法,其中混合物被制成成型制品,该自由基聚合条件包括施加足以使该成型制品交联的热量。
19、包括一种混合物的固化反应产物的聚合物组合物,该混合物包括
a)弹性体聚合物,它含有约0.01-约10mol%沿弹性体聚合物链和侧挂于聚合物链的无规分布的Y酯基,该Y酯基具有以下结构:其中R2和R3独立地选自氢和含有1-约6个碳原子的烷基和R4选自氢,含有1-约28个碳原子的烷基,芳基和含有2-约28个碳原子的链烯基;和
b)至少一种可自由基聚合的单体;
20、权利要求19的组合物,其中弹性聚合物是包括至少约80wt%含有4-7个碳原子的聚合异烯烃和约0.05-约20wt%包含以下无规分布结构的混合结构的芳族单体单元的无规共聚物:其中R和R′独立地选自氢和C1-C4烷基。
21、权利要求20的组合物,其中混合物进一步含有自由基引发剂。
22、权利要求20的组合物,其中C4-C7异烯烃是异丁烯和该共聚物含有至少约90wt%异丁烯,其中R和R′各自是氢。
23、权利要求22的组合物,其中R2是甲基及R3和R4各自是氢。
24、权利要求22的组合物,其中R2、R3和R4各自是氢。
25、权利要求22的组合物,其中R2和R3各自是氢和R4是C4链烯基。
26、权利要求20的组合物,其中含有约0.05-约2.0mol%Y酯基。
27、权利要求20的组合物,其中该混合芳族单体单元的约5-约60mol%含有结构(b)。
28、权利要求20的组合物,其中该弹性共聚物的数均分子量为约25,000-约1,000,000,组成分布(Mw/Mn)低于约7。
29、权利要求20的组合物,其中可自由基聚合的单体在混合物中以约1-100重量份/100重量份弹性共聚物的量存在。
30、权利要求29的组合物,其中所述单体包括从苯乙烯和取代的苯乙烯,丙烯酸和甲基丙烯酸烷基酯,丙烯酸,甲基丙烯酸,丙烯腈,甲基丙烯腈,乙烯基酯,乙烯基醚,丙烯酰胺,甲基丙烯酰胺,乙烯基咔唑,氯乙烯,乙酸乙烯酯,乙烯基吡啶,乙烯基吡咯烷酮,马来酸或酸酐以及它们的混合物中选择的单官能度单体。
31、权利要求29的组合物,其中所述单体进一步包括从丁二烯,异戊二烯,二或三乙烯基苯,二或三丙烯酸或甲基丙烯酸亚烷基二醇酯及其混合物中选择的多官能度单体。
32、权利要求20的组合物,其中所述混合物进一步含有选自有机过氧化物和氢过氧化物的自由基引发剂。
33、权利要求20的组合物,其中所述固化反应产物通过让所述混合物经受自由基聚合条件而制备。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/469,285 | 1995-06-06 | ||
US08/469,285 US5567775A (en) | 1989-11-27 | 1995-06-06 | Craft curing of modified isomonoolefin/para-alkylstyrene copolymers |
Publications (1)
Publication Number | Publication Date |
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CN1190976A true CN1190976A (zh) | 1998-08-19 |
Family
ID=23863205
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN96195545A Pending CN1190976A (zh) | 1995-06-06 | 1996-06-06 | 改性异单烯烃/对烷基苯乙烯共聚物的接枝固化 |
Country Status (14)
Country | Link |
---|---|
US (1) | US5567775A (zh) |
EP (1) | EP0830401A1 (zh) |
JP (1) | JPH11502254A (zh) |
KR (1) | KR19990022428A (zh) |
CN (1) | CN1190976A (zh) |
BR (1) | BR9608952A (zh) |
CA (1) | CA2220666A1 (zh) |
CZ (1) | CZ385297A3 (zh) |
EA (1) | EA199800022A1 (zh) |
HU (1) | HUP9901100A3 (zh) |
MX (1) | MX9709603A (zh) |
PL (1) | PL323734A1 (zh) |
TW (1) | TW332819B (zh) |
WO (1) | WO1996039452A1 (zh) |
Cited By (3)
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CN103228681A (zh) * | 2010-11-24 | 2013-07-31 | 朗盛公司 | 包含侧链乙烯基的磷离子交联聚合物及其制备方法 |
CN108350115A (zh) * | 2015-09-30 | 2018-07-31 | 埃克森美孚化学专利公司 | 异丁烯共聚物主链与官能聚合物梳形臂的梳形-嵌段共聚物 |
CN109219642A (zh) * | 2016-06-03 | 2019-01-15 | 赛鲁斯股份有限公司 | 用末端1,1-二取代烯烃单体官能化的聚合物和其他化合物及其方法 |
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AU734767B2 (en) * | 1997-01-27 | 2001-06-21 | Mitsui Chemicals, Inc. | Adhesive resin compositions and laminates using the compositions for adhesive layers |
KR20010032104A (ko) * | 1997-12-15 | 2001-04-16 | 엑손 케미칼 패턴츠 인코포레이티드 | 투명하고 착색가능한 탄성중합체성 조성물 |
EP1266912B1 (en) * | 2001-06-15 | 2008-12-17 | JSR Corporation | (Meth)acryloyl group-modified ethylene-alpha-olefin copolymer, production method thereof and rubber composition |
US7509913B1 (en) * | 2003-05-14 | 2009-03-31 | Franklin Eagle | Table bridge |
US8597784B2 (en) | 2010-09-30 | 2013-12-03 | 3M Innovative Properties Company | Radiation curable poly(isobutylene) adhesive copolymers |
KR101909760B1 (ko) | 2010-11-16 | 2018-10-18 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Uv 경화성 무수물-개질 폴리(아이소부틸렌) |
US8663407B2 (en) | 2010-11-17 | 2014-03-04 | 3M Innovative Properties Company | Isobutylene (Co)polymeric adhesive composition |
US8629209B2 (en) | 2010-12-02 | 2014-01-14 | 3M Innovative Properties Company | Moisture curable isobutylene adhesive copolymers |
US8673995B2 (en) | 2011-06-20 | 2014-03-18 | 3M Innovative Properties Company | Radiation curable poly(isobutylene) adhesive copolymers having pendent amine groups |
WO2016190358A1 (ja) | 2015-05-26 | 2016-12-01 | 株式会社カネカ | 熱可塑性エラストマーの製造方法及び熱可塑性エラストマー |
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US3489822A (en) * | 1962-08-31 | 1970-01-13 | Uniroyal Inc | Grafted terpolymer of ethylene,propylene and a non-conjugated diene |
US3968185A (en) * | 1974-12-09 | 1976-07-06 | Baldwin Francis P | Preparation of modified elastomers |
JPS59199785A (ja) * | 1983-04-27 | 1984-11-12 | Showa Highpolymer Co Ltd | 嫌気硬化性を有する粘着材 |
JPS62153340A (ja) * | 1985-12-27 | 1987-07-08 | Showa Highpolymer Co Ltd | 硬化性組成物 |
US5162445A (en) * | 1988-05-27 | 1992-11-10 | Exxon Chemical Patents Inc. | Para-alkylstyrene/isoolefin copolymers and functionalized copolymers thereof |
EP0353471B1 (en) * | 1988-08-05 | 1994-01-05 | Edison Polymer Innovation Corporation ( Epic) | UV curable polymer formulation |
US5206303A (en) * | 1990-12-27 | 1993-04-27 | Exxon Chemical Patents Inc. | Entanglement-inhibited macromolecules |
ES2118838T3 (es) * | 1991-10-17 | 1998-10-01 | Exxon Chemical Patents Inc | Copolimeros de isoolefina curables por radiacion. |
WO1995002003A1 (en) * | 1993-07-08 | 1995-01-19 | Avery Dennison Corporation | Acrylic-saturated rubber hybrid pressure-sensitive adhesives |
-
1995
- 1995-06-06 US US08/469,285 patent/US5567775A/en not_active Expired - Fee Related
-
1996
- 1996-06-06 BR BR9608952A patent/BR9608952A/pt unknown
- 1996-06-06 HU HU9901100A patent/HUP9901100A3/hu unknown
- 1996-06-06 KR KR1019970708908A patent/KR19990022428A/ko not_active Application Discontinuation
- 1996-06-06 WO PCT/US1996/009829 patent/WO1996039452A1/en not_active Application Discontinuation
- 1996-06-06 MX MX9709603A patent/MX9709603A/es not_active Application Discontinuation
- 1996-06-06 CA CA002220666A patent/CA2220666A1/en not_active Abandoned
- 1996-06-06 PL PL96323734A patent/PL323734A1/xx unknown
- 1996-06-06 JP JP9502033A patent/JPH11502254A/ja active Pending
- 1996-06-06 CN CN96195545A patent/CN1190976A/zh active Pending
- 1996-06-06 EA EA199800022A patent/EA199800022A1/ru unknown
- 1996-06-06 CZ CZ973852A patent/CZ385297A3/cs unknown
- 1996-06-06 EP EP96918418A patent/EP0830401A1/en not_active Withdrawn
- 1996-09-16 TW TW085111297A patent/TW332819B/zh active
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103228681A (zh) * | 2010-11-24 | 2013-07-31 | 朗盛公司 | 包含侧链乙烯基的磷离子交联聚合物及其制备方法 |
CN103228681B (zh) * | 2010-11-24 | 2016-01-20 | 朗盛公司 | 包含侧链乙烯基的磷离子交联聚合物及其制备方法 |
CN108350115A (zh) * | 2015-09-30 | 2018-07-31 | 埃克森美孚化学专利公司 | 异丁烯共聚物主链与官能聚合物梳形臂的梳形-嵌段共聚物 |
CN109219642A (zh) * | 2016-06-03 | 2019-01-15 | 赛鲁斯股份有限公司 | 用末端1,1-二取代烯烃单体官能化的聚合物和其他化合物及其方法 |
Also Published As
Publication number | Publication date |
---|---|
CZ385297A3 (cs) | 1998-05-13 |
US5567775A (en) | 1996-10-22 |
BR9608952A (pt) | 1999-03-02 |
TW332819B (en) | 1998-06-01 |
WO1996039452A1 (en) | 1996-12-12 |
EA199800022A1 (ru) | 1998-08-27 |
JPH11502254A (ja) | 1999-02-23 |
HUP9901100A3 (en) | 2000-02-28 |
HUP9901100A2 (hu) | 1999-07-28 |
KR19990022428A (ko) | 1999-03-25 |
MX9709603A (es) | 1998-04-30 |
PL323734A1 (en) | 1998-04-14 |
CA2220666A1 (en) | 1996-12-12 |
EP0830401A1 (en) | 1998-03-25 |
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